Organic electroluminescent materials and devices

ABSTRACT

A method of making an osmium(II) complex having Formula I, L 1 -Os-L 2 , wherein L 1  and L 2  are independently a biscarbene tridentate ligand, wherein L 1  and L 2  can be same or different is disclosed. The method includes (a) reacting a precursor of ligand L 1  with an osmium precursor to form an intermediate product, wherein the osmium precursor having the formula OsH x (PR 3 ) y , wherein x is an integer from 2 to 6 and y is an integer from 2 to 5, and R is selected from the group consisting of aryl, alkyl and cycloalkyl; and (b) reacting a precursor of ligand L 2  with said intermediate product.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. application Ser. No.13/950,591, filed Jul. 25, 2013, the entirety of which is incorporatedherein by reference.

PARTIES TO A JOINT RESEARCH AGREEMENT

The claimed invention was made by, on behalf of, and/or in connectionwith one or more of the following parties to a joint universitycorporation research agreement: Regents of the University of Michigan,Princeton University, University of Southern California, and theUniversal Display Corporation. The agreement was in effect on and beforethe date the claimed invention was made, and the claimed invention wasmade as a result of activities undertaken within the scope of theagreement.

FIELD OF THE INVENTION

The present invention relates to compounds for use as emitters anddevices, such as organic light emitting diodes, including the same. Moreparticularly, the compounds disclosed herein are novel heterolepticbistridentate osmium carbene complexes and a novel synthetic method tomake both homoleptic and heteroleptic bistridentate osmium carbenecomplexes.

BACKGROUND

Opto-electronic devices that make use of organic materials are becomingincreasingly desirable for a number of reasons. Many of the materialsused to make such devices are relatively inexpensive, so organicopto-electronic devices have the potential for cost advantages overinorganic devices. In addition, the inherent properties of organicmaterials, such as their flexibility, may make them well suited forparticular applications such as fabrication on a flexible substrate.Examples of organic opto-electronic devices include organic lightemitting devices (OLEDs), organic phototransistors, organic photovoltaiccells, and organic photodetectors. For OLEDs, the organic materials mayhave performance advantages over conventional materials. For example,the wavelength at which an organic emissive layer emits light maygenerally be readily tuned with appropriate dopants.

OLEDs make use of thin organic films that emit light when voltage isapplied across the device. OLEDs are becoming an increasinglyinteresting technology for use in applications such as flat paneldisplays, illumination, and backlighting. Several OLED materials andconfigurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emissive molecules is a full colordisplay. Industry standards for such a display call for pixels adaptedto emit particular colors, referred to as “saturated” colors. Inparticular, these standards call for saturated red, green, and bluepixels. Color may be measured using CIE coordinates, which are wellknown to the art.

One example of a green emissive molecule is tris(2-phenylpyridine)iridium, denoted Ir(ppy)₃, which has the following structure:

In this, and later figures herein, we depict the dative bond fromnitrogen to metal (here, Ir) as a straight line.

As used herein, the term “organic” includes polymeric materials as wellas small molecule organic materials that may be used to fabricateorganic opto-electronic devices. “Small molecule” refers to any organicmaterial that is not a polymer, and “small molecules” may actually bequite large. Small molecules may include repeat units in somecircumstances. For example, using a long chain alkyl group as asubstituent does not remove a molecule from the “small molecule” class.Small molecules may also be incorporated into polymers, for example as apendent group on a polymer backbone or as a part of the backbone. Smallmolecules may also serve as the core moiety of a dendrimer, whichconsists of a series of chemical shells built on the core moiety. Thecore moiety of a dendrimer may be a fluorescent or phosphorescent smallmolecule emitter. A dendrimer may be a “small molecule,” and it isbelieved that all dendrimers currently used in the field of OLEDs aresmall molecules.

As used herein, “top” means furthest away from the substrate, while“bottom” means closest to the substrate. Where a first layer isdescribed as “disposed over” a second layer, the first layer is disposedfurther away from substrate. There may be other layers between the firstand second layer, unless it is specified that the first layer is “incontact with” the second layer. For example, a cathode may be describedas “disposed over” an anode, even though there are various organiclayers in between.

As used herein, “solution processible” means capable of being dissolved,dispersed, or transported in and/or deposited from a liquid medium,either in solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed thatthe ligand directly contributes to the photoactive properties of anemissive material. A ligand may be referred to as “ancillary” when it isbelieved that the ligand does not contribute to the photoactiveproperties of an emissive material, although an ancillary ligand mayalter the properties of a photoactive ligand.

As used herein, and as would be generally understood by one skilled inthe art, a first “Highest Occupied Molecular Orbital” (HOMO) or “LowestUnoccupied Molecular Orbital” (LUMO) energy level is “greater than” or“higher than” a second HOMO or LUMO energy level if the first energylevel is closer to the vacuum energy level. Since ionization potentials(IP) are measured as a negative energy relative to a vacuum level, ahigher HOMO energy level corresponds to an IP having a smaller absolutevalue (an IP that is less negative). Similarly, a higher LUMO energylevel corresponds to an electron affinity (EA) having a smaller absolutevalue (an EA that is less negative). On a conventional energy leveldiagram, with the vacuum level at the top, the LUMO energy level of amaterial is higher than the HOMO energy level of the same material. A“higher” HOMO or LUMO energy level appears closer to the top of such adiagram than a “lower” HOMO or LUMO energy level.

As used herein, and as would be generally understood by one skilled inthe art, a first work function is “greater than” or “higher than” asecond work function if the first work function has a higher absolutevalue. Because work functions are generally measured as negative numbersrelative to vacuum level, this means that a “higher” work function ismore negative. On a conventional energy level diagram, with the vacuumlevel at the top, a “higher” work function is illustrated as furtheraway from the vacuum level in the downward direction. Thus, thedefinitions of HOMO and LUMO energy levels follow a different conventionthan work functions.

More details on OLEDs, and the definitions described above, can be foundin U.S. Pat. No. 7,279,704, which is incorporated herein by reference inits entirety.

SUMMARY OF THE INVENTION

According to an aspect of the present disclosure, a method of making anosmium(II) complex having Formula I

L¹-Os-L², wherein L¹ and L² are independently a biscarbene tridentateligand, wherein L¹ and L² can be same or different is disclosed. Themethod comprises: (a) reacting a precursor of ligand L¹ with an osmiumprecursor to form an intermediate product, wherein the osmium precursorhaving the formula OsH_(x)(PR₃)_(y), wherein x is an integer from 2 to 6and y is an integer from 2 to 5, and R is selected from the groupconsisting of aryl, alkyl and cycloalkyl; and (b) reacting a precursorof ligand L² with said intermediate product.

In one embodiment of the method, L¹ and L² are monoanionic ligands. Insome embodiments, L¹ and L² are independently selected from ligandshaving Formula II:

wherein Y¹, Y² and Y³ comprise C or N; wherein R³ and R⁴ may representmono-, or di-substitutions, or no substitution; wherein R⁵ may representmono-, di-, or tri-substitutions, or no substitution; wherein R¹, R²,R³, R⁴ and R⁵ are independently selected from the group consisting ofhydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl,alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester,nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof; wherein any two adjacent substituents of R¹, R²,R³, R⁴ and R⁵ are optionally joined to form a ring; and wherein the dashlines show the connection points to osmium.

According to an embodiment, a compound having the structure according toFormula I as defined herein is disclosed.

According to another aspect of the present disclosure, a first devicecomprising a first organic light emitting device is disclosed. The firstorganic light emitting device comprises an anode; a cathode; and anorganic layer, disposed between the anode and the cathode. The organiclayer can comprise a compound having the structure according Formula I

The novel compounds, heteroleptic bistridentate osmium carbenecomplexes, and a novel synthetic method to make both homoleptic andheteroleptic bistridentate osmium carbene complexes disclosed herein areuseful as emitters in organic light emitting devices. The inventors havediscovered that the incorporation of these ligands can narrow theemission spectrum and improve device efficiency.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does nothave a separate electron transport layer.

FIG. 3 shows molecular diagram of complex monohydride with X-raydiffraction analysis characterization.

FIG. 4 shows molecular diagram of Complex A with X-ray diffractionanalysis characterization.

DETAILED DESCRIPTION

Generally, an OLED comprises at least one organic layer disposed betweenand electrically connected to an anode and a cathode. When a current isapplied, the anode injects holes and the cathode injects electrons intothe organic layer(s). The injected holes and electrons each migratetoward the oppositely charged electrode. When an electron and holelocalize on the same molecule, an “exciton,” which is a localizedelectron-hole pair having an excited energy state, is formed. Light isemitted when the exciton relaxes via a photoemissive mechanism. In somecases, the exciton may be localized on an excimer or an exciplex.Non-radiative mechanisms, such as thermal relaxation, may also occur,but are generally considered undesirable.

The initial OLEDs used emissive molecules that emitted light from theirsinglet states (“fluorescence”) as disclosed, for example, in U.S. Pat.No. 4,769,292, which is incorporated by reference in its entirety.Fluorescent emission generally occurs in a time frame of less than 10nanoseconds.

More recently, OLEDs having emissive materials that emit light fromtriplet states (“phosphorescence”) have been demonstrated. Baldo et al.,“Highly Efficient Phosphorescent Emission from OrganicElectroluminescent Devices,” Nature, vol. 395, 151-154, 1998;(“Baldo-I”) and Baldo et al., “Very high-efficiency green organiclight-emitting devices based on electrophosphorescence,” Appl. Phys.Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporatedby reference in their entireties. Phosphorescence is described in moredetail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporatedby reference.

FIG. 1 shows an organic light emitting device 100. The figures are notnecessarily drawn to scale. Device 100 may include a substrate 110, ananode 115, a hole injection layer 120, a hole transport layer 125, anelectron blocking layer 130, an emissive layer 135, a hole blockinglayer 140, an electron transport layer 145, an electron injection layer150, a protective layer 155, a cathode 160, and a barrier layer 170.Cathode 160 is a compound cathode having a first conductive layer 162and a second conductive layer 164. Device 100 may be fabricated bydepositing the layers described, in order. The properties and functionsof these various layers, as well as example materials, are described inmore detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which areincorporated by reference.

More examples for each of these layers are available. For example, aflexible and transparent substrate-anode combination is disclosed inU.S. Pat. No. 5,844,363, which is incorporated by reference in itsentirety. An example of a p-doped hole transport layer is m-MTDATA dopedwith F₄-TCNQ at a molar ratio of 50:1, as disclosed in U.S. PatentApplication Publication No. 2003/0230980, which is incorporated byreference in its entirety. Examples of emissive and host materials aredisclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which isincorporated by reference in its entirety. An example of an n-dopedelectron transport layer is BPhen doped with Li at a molar ratio of 1:1,as disclosed in U.S. Patent Application Publication No. 2003/0230980,which is incorporated by reference in its entirety. U.S. Pat. Nos.5,703,436 and 5,707,745, which are incorporated by reference in theirentireties, disclose examples of cathodes including compound cathodeshaving a thin layer of metal such as Mg:Ag with an overlyingtransparent, electrically-conductive, sputter-deposited ITO layer. Thetheory and use of blocking layers is described in more detail in U.S.Pat. No. 6,097,147 and U.S. Patent Application Publication No.2003/0230980, which are incorporated by reference in their entireties.Examples of injection layers are provided in U.S. Patent ApplicationPublication No. 2004/0174116, which is incorporated by reference in itsentirety. A description of protective layers may be found in U.S. PatentApplication Publication No. 2004/0174116, which is incorporated byreference in its entirety.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210,a cathode 215, an emissive layer 220, a hole transport layer 225, and ananode 230. Device 200 may be fabricated by depositing the layersdescribed, in order. Because the most common OLED configuration has acathode disposed over the anode, and device 200 has cathode 215 disposedunder anode 230, device 200 may be referred to as an “inverted” OLED.Materials similar to those described with respect to device 100 may beused in the corresponding layers of device 200. FIG. 2 provides oneexample of how some layers may be omitted from the structure of device100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided byway of non-limiting example, and it is understood that embodiments ofthe invention may be used in connection with a wide variety of otherstructures. The specific materials and structures described areexemplary in nature, and other materials and structures may be used.Functional OLEDs may be achieved by combining the various layersdescribed in different ways, or layers may be omitted entirely, based ondesign, performance, and cost factors. Other layers not specificallydescribed may also be included. Materials other than those specificallydescribed may be used. Although many of the examples provided hereindescribe various layers as comprising a single material, it isunderstood that combinations of materials, such as a mixture of host anddopant, or more generally a mixture, may be used. Also, the layers mayhave various sublayers. The names given to the various layers herein arenot intended to be strictly limiting. For example, in device 200, holetransport layer 225 transports holes and injects holes into emissivelayer 220, and may be described as a hole transport layer or a holeinjection layer. In one embodiment, an OLED may be described as havingan “organic layer” disposed between a cathode and an anode. This organiclayer may comprise a single layer, or may further comprise multiplelayers of different organic materials as described, for example, withrespect to FIGS. 1 and 2.

Structures and materials not specifically described may also be used,such as OLEDs comprised of polymeric materials (PLEDs) such as disclosedin U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated byreference in its entirety. By way of further example, OLEDs having asingle organic layer may be used. OLEDs may be stacked, for example asdescribed in U.S. Pat. No. 5,707,745 to Forrest et al, which isincorporated by reference in its entirety. The OLED structure maydeviate from the simple layered structure illustrated in FIGS. 1 and 2.For example, the substrate may include an angled reflective surface toimprove out-coupling, such as a mesa structure as described in U.S. Pat.No. 6,091,195 to Forrest et al., and/or a pit structure as described inU.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated byreference in their entireties.

Unless otherwise specified, any of the layers of the various embodimentsmay be deposited by any suitable method. For the organic layers,preferred methods include thermal evaporation, ink-jet, such asdescribed in U.S. Pat. Nos. 6,013,982 and 6,087,196, which areincorporated by reference in their entireties, organic vapor phasedeposition (OVPD), such as described in U.S. Pat. No. 6,337,102 toForrest et al., which is incorporated by reference in its entirety, anddeposition by organic vapor jet printing (OVJP), such as described inU.S. Pat. No. 7,431,968, which is incorporated by reference in itsentirety. Other suitable deposition methods include spin coating andother solution based processes. Solution based processes are preferablycarried out in nitrogen or an inert atmosphere. For the other layers,preferred methods include thermal evaporation. Preferred patterningmethods include deposition through a mask, cold welding such asdescribed in U.S. Pat. Nos. 6,294,398 and 6,468,819, which areincorporated by reference in their entireties, and patterning associatedwith some of the deposition methods such as ink-jet and OVJD. Othermethods may also be used. The materials to be deposited may be modifiedto make them compatible with a particular deposition method. Forexample, substituents such as alkyl and aryl groups, branched orunbranched, and preferably containing at least 3 carbons, may be used insmall molecules to enhance their ability to undergo solution processing.Substituents having 20 carbons or more may be used, and 3-20 carbons isa preferred range. Materials with asymmetric structures may have bettersolution processibility than those having symmetric structures, becauseasymmetric materials may have a lower tendency to recrystallize.Dendrimer substituents may be used to enhance the ability of smallmolecules to undergo solution processing.

Devices fabricated in accordance with embodiments of the presentinvention may further optionally comprise a barrier layer. One purposeof the barrier layer is to protect the electrodes and organic layersfrom damaging exposure to harmful species in the environment includingmoisture, vapor and/or gases, etc. The barrier layer may be depositedover, under or next to a substrate, an electrode, or over any otherparts of a device including an edge. The barrier layer may comprise asingle layer, or multiple layers. The barrier layer may be formed byvarious known chemical vapor deposition techniques and may includecompositions having a single phase as well as compositions havingmultiple phases. Any suitable material or combination of materials maybe used for the barrier layer. The barrier layer may incorporate aninorganic or an organic compound or both. The preferred barrier layercomprises a mixture of a polymeric material and a non-polymeric materialas described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos.PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporatedby reference in their entireties. To be considered a “mixture”, theaforesaid polymeric and non-polymeric materials comprising the barrierlayer should be deposited under the same reaction conditions and/or atthe same time. The weight ratio of polymeric to non-polymeric materialmay be in the range of 95:5 to 5:95. The polymeric material and thenon-polymeric material may be created from the same precursor material.In one example, the mixture of a polymeric material and a non-polymericmaterial consists essentially of polymeric silicon and inorganicsilicon.

Devices fabricated in accordance with embodiments of the invention maybe incorporated into a wide variety of consumer products, including flatpanel displays, computer monitors, medical monitors, televisions,billboards, lights for interior or exterior illumination and/orsignaling, heads up displays, fully transparent displays, flexibledisplays, laser printers, telephones, cell phones, personal digitalassistants (PDAs), laptop computers, digital cameras, camcorders,viewfinders, micro-displays, 3-D displays, vehicles, a large area wall,theater or stadium screen, or a sign. Various control mechanisms may beused to control devices fabricated in accordance with the presentinvention, including passive matrix and active matrix. Many of thedevices are intended for use in a temperature range comfortable tohumans, such as 18 degrees C. to 30 degrees C., and more preferably atroom temperature (20-25 degrees C.), but could be used outside thistemperature range, for example, from −40 degree C. to +80 degree C.

The materials and structures described herein may have applications indevices other than OLEDs. For example, other optoelectronic devices suchas organic solar cells and organic photodetectors may employ thematerials and structures. More generally, organic devices, such asorganic transistors, may employ the materials and structures.

The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl,heterocyclic group, aryl, aromatic group, and heteroaryl are known tothe art, and are defined in U.S. Pat. No. 7,279,704 at cols. 31-32,which are incorporated herein by reference.

As used herein, “substituted” indicates that a substituent other than His bonded to the relevant carbon. Thus, where R² is monosubstituted,then one R² must be other than H. Similarly, where R³ is disubstituted,then two of R³ must be other than H. Similarly, where R² isunsubstituted R² is hydrogen for all available positions.

In the present disclosure, novel heteroleptic bistridentate Os(II)complexes and a novel method for synthesizing both homoleptic andheteroleptic bistridentate Os(II) complexes is provided. Heterolepticosmium complexes provide great freedom of tuning emission color,electrochemical energy levels, and improving evaporation properties.

Osmium (II) complexes have been investigated for OLED applications. Theoctahedral ligand arrangement of the Os(II) complexes resembles that ofIr(III) complexes. Os(II) complexes generally exhibit low oxidationpotential, i.e. shallow HOMO energy level than Ir(III) complexes. Theinventors have discovered that bistridentate Os(II) carbene complexesoffer performance advantages for OLED applications. Without being boundto a theory, the inventors believe that the rigid nature of thetridentate ligands are providing narrow emission line widths and shortexcited state lifetimes, which can result in better color purity andlonger device lifetime, making them suitable for display applications.

US2005260449 and WO2009046266 disclosed bistridentate Os(II) complexes.Examples of homoleptic Os(II) complexes were provided. The twotridentate ligands binding to Os(II) metal are identical. It may bebeneficial to incorporate two different ligands to Os(II) metal to forma heterlopetic complex. For example, the thermal properties,electrochemical properties, and photophysical properties can be tuned byselecting two proper ligands. It offers more flexibility for materialsdesign than two identical ligands.

The synthesis of homoleptic complexes, however, has been challenging;let alone the heteroleptic complexes. The synthesis method used inWO2009046266 generated very low yield, typically 2-5%. In a laterapplication, US2012215000, the yield was significantly improved to over30% using a new osmium precursor. In theory, both of these methodsshould work for synthesis of heteroleptic bistridentate Os(II) complexesby introducing two different ligands at the complexation stage andisolating the desired heteroleptic complex from the reaction mixture.The synthesis will be extremely inefficient and impractical.

The inventors have developed a new stepwise complexation method. Thismethod is suitable for making both homoleptic and heterolepticbistridentate Os(II) complexes. As shown in the scheme below, an osmiumprecursor was first reacted with a bistridentate ligand to generate anintermediate that has one tridentate ligand coordinated to the metal.The intermediate was then treated with another tridentate ligand togenerate the final complex. Depending on the structure of the secondligand, homoleptic or heteroleptic complexes can be synthesized. Inaddition, the yield was improved. One example of the inventive syntheticmethod is shown below:

In describing the novel synthesis method of the inventors, all reactionswere carried out with rigorous exclusion of air using Schlenk-tubetechniques. Solvents, except DMF and acetonitrile that were dried anddistilled under argon, were obtained oxygen- and water-free from anMBraun solvent purification apparatus. ¹H ³¹P{¹H}, ¹⁹F and ¹³C{¹H} NMRspectra were recorded on Bruker 300 ARX, Bruker Avance 300 MHz, andBruker Avance 400 MHz instruments. Chemical shifts (expressed in partsper million) are referenced to residual solvent peaks (¹H, ¹³C{¹H}) orexternal 85% H₃PO₄ (³¹P{¹H}), or external CFCl₃ (¹⁹F). Couplingconstants J and N are given in hertz. Attenuated total reflectioninfrared spectra (ATR-IR) of solid samples were run on a Perkin-ElmerSpectrum 100 FT-IR spectrometer. C, H, and N analyses were carried outin a Perkin-Elmer 2400 CHNS/O analyzer. High-resolution electrospraymass spectra were acquired using a MicroTOF-Q hybrid quadrupoletime-of-flight spectrometer (Bruker Daltonics, Bremen, Germany).OsH₆(P^(i)Pr₃)₂ was prepared by the method published in Aracama, M.;Esteruelas, M. A.; Lahoz, F. J.; López, J. A.; Meyer, U.; Oro, L. A.;Werner, H. Inorg. Chem. 1991, 30, 288.

Preparation of Dihydride-BF4

A solution of OsH₆(P^(i)Pr₃)₂ (261 mg, 0.505 mmol) in dimethylformamide(DMF) (5 mL) was treated with1,3-bis[(1-methyl)benzylimidazolium-3-yl]benzene diiodide (300 mg, 0.505mmol). The resulting mixture was refluxed for 20 min, getting a verydark solution. After cooling at room temperature the solvent was removedin vacuo, affording a dark residue. The residue was dissolved inacetonitrile (10 mL) and AgBF₄ (98.3 mg, 0.505 mmol) was added. Afterstirring protected from the light for 30 min the resulting suspensionwas filtered through Celite to remove the silver salts. The solutionthus obtained was evaporated to ca. 0.5 mL and diethyl ether (10 mL) wasadded to afford a beige solid, that was washed with further portions ofdiethyl ether (2×2 mL) and dried in vacuo. Yield: 240 mg (50%).Analytical Calculation for C₄₀H₆₁BF₄N₄OsP₂: C, 51.28; H, 6.56; N, 5.98.Found: C, 51.55; H, 6.70; N, 5.62. HRMS (electrospray, m/z): calcd forC₄₀H₆₁N₄OsP₂ [M]⁺: 851.3983; found: 851.4036. IR (cm⁻¹): ν(Os—H) 2104(w), ν(BF₄) 1080-1000 (vs). ¹H NMR (300 MHz, CD₃CN, 298K): δ 8.31 (m,2H, CH bzm), 7.98 (d, J_(H—H)=7.9, 2H, CH Ph), 7.70 (m, 2H, CH bzm),7.57 (t, J_(H—H)=7.9, 1H, CH Ph), 7.54-7.50 (m, 4H, CH bzm), 4.32 (s,6H, CH₃), 1.54 (m, 6H, PCH(CH₃)₂), 0.67 (dvt, J_(HH)=6.2, N=13.2, 36H,PCH(CH₃)₂), −6.25 (t, J_(H—P)=13.6, 2H, Os—H). ¹³C{¹H} NMR (75.42 MHz,CD₃CN, 293K): δ 189.4 (t, J_(C—P)=7.5, NCN), 161.3 (Os—C), 146.9 (s, CPh), 137.3 (s, C Bzm), 132.8 (s, C Bzm), 124.9 (s, CH Bzm), 124.5 (s, CHBzm), 124.2 (s, CH Ph), 112.8 (s, CH Bzm), 111.9 (s, CH Bzm), 109.2 (s,CH Ph), 38.9 (s, CH₃), 29.3 (t, N=27, PCH(CH₃)₂), 18.5 (s, PCH(CH₃)₂).³¹P{¹H} NMR (121.4 MHz, CD₃CN, 293K): δ 4.5 (s).

Preparation of complex monohydride, shown below:

This monohydride compound can be prepared by using two differentmethods. Method (A): A solution of OsH₆(P^(i)Pr₃)₂ (261 mg, 0.505 mmol)in DMF (5 mL) was treated with1,3-bis[(1-methyl)benzylimidazolium-3-yl]benzene diiodide (300 mg, 0.505mmol). The resulting mixture was refluxed for 20 min, getting a verydark solution. After cooling at room temperature the solvent was removedin vacuo, affording a dark residue. The dark residue was dissolved in 10mL of tetrahydrofuran (THF) and K^(t)BuO (142 mg, 1.263 mmol) was addedto the solution. After stirring at room temperature for 10 min theresulting suspension was filtered through Celite to remove the potassiumsalts. The solution thus obtained was evaporated to dryness to afford ayellow residue. Addition of pentane afforded a yellow solid, which waswashed with pentane (1×2 mL) and dried in vacuo to obtain a yellowsolid. Yield: 378 mg (88%). Method (B): A solution of dihydride-BF4 (200mg, 0.213 mmol) in THF (5 mL) was treated with K^(t)BuO (28.6 mg, 0.255mmol). After stirring at room temperature for 10 min the resultingsuspension was filtered through Celite to remove the potassium salts.The solution thus obtained was evaporated to dryness to afford a yellowresidue. Addition of pentane afforded a yellow solid, which was washedwith pentane (1×2 mL) and dried in vacuo obtain a yellow solid. Yield:163 mg (90%). Anal. Calcd. for C₄₀H₆₀N₄OsP₂: C, 56.58; H, 7.12; N, 6.60.Found: C, 56.00; H, 6.69; N, 6.76. HRMS (electrospray, m/z): calcd. For[M+H]⁺ 851.3983; found: 851.3979. IR (cm⁻¹): ν(Os—H) 1889 (w). ¹H NMR(300 MHz, C₆D₆, 298K): δ 8.17 (d, J_(H—H)=7.7, 2H, CH Ph), 8.06 (d,J_(H—H)=7.7, 2H, CH bzm), 7.60 (t, J_(H—H)=7.7, 1H, CH Ph), 7.20 (td,J_(H—H)=7.9, J_(H—H)=1.0, 2H, CH bzm), 7.14-7.03 (m, 4H CH bzm), 3.92(s, 6H, CH₃), 1.55 (m, 6H, PCH(CH₃)₂), 0.67 (dvt, J_(H.H)=6.9, N=12.3,36H, PCH(CH₃)₂), −9.55 (t, J_(H—P)=33.6, 1H, Os—H). ¹³C{¹H} NMR (75.42MHz, C₆D₆, 293K): δ 197.6 (t, J_(C—P)=9.2, Os—NCN), 173.2 (t,J_(C—P)=2.9, Os—C), 148.4 (s, C Ph), 137.3 (s, C Bzm), 134.4 (s, C Bzm),121.5 (s, CH Bzm), 121.2 (s, CH Bzm), 117.9 (s, CH Ph), 109.6 (s, CHBzm), 108.5 (s, CH Bzm), 105.8 (s, CH Ph), 37.9 (s, CH₃), 31.0 (t,N=24.2, PCH(CH₃)₂), 19.7 (s, PCH(CH₃)₂). ³¹P{¹H} NMR (121.4 MHz, C₆D₆,293K): δ 20.6 (s, doublet under off resonance conditions). FIG. 3 showsthe molecular structure of complex monohydride with the X-raydiffraction analysis characterization. Selected bond lengths (Å) andangles (°) were: Os—P(1)=2.3512(18), Os—P(2)=2.3529(17),Os—C(1)=2.052(6), Os—C(9)=2.036(3), Os—C(15)=2.035(6);P(1)-Os—P(2)=152.86(6), C(1)-Os—C(9)=75.5(2), C(9)-Os—C(15)=75.4(2),C(1)-Os(C15)=150.9(2).

Preparation of Complex Monohydride-CF3:

Method (A):

A solution of dihydride-CF3-BF4 (200 mg, 0.2 mmol) in THF (5 mL) wastreated with K^(t)BuO (26.8 mg, 0.24 mmol). After stirring at roomtemperature for 10 min the resulting suspension was filtered throughCelite to remove the potassium salts. The solution thus obtained wasevaporated to dryness to afford a yellow residue. Addition of pentaneafforded a yellow solid, which was washed with pentane (1×2 mL) anddried in vacuo obtain a yellow solid. Yield: 240 mg (50%). Anal. Calcd.for C₄₁H₅₉F₃N₄OsP₂: C, 53.69; H, 6.48; N, 6.11. Found: C, 53.20; H,6.33; N, 6.18. IR (cm⁻¹): ν(Os—H) 1842 (w). ¹H NMR (300 MHz, C₆D₆,298K): δ 8.53 (s, 2H, CH Ph-CF₃), 8.18 (m, 2H, CH bzm), 7.15-6.98 (m,6H, CH bzm), 3.86 (s, 6H, CH₃), 1.49 (m, 6H, PCH(CH₃)₂), 0.60 (dvt,J_(H.H)=6.6, N=12.9, 36H, PCH(CH₃)₂), −9.29 (t, J_(H—P)=34.0, 1H, Os—H).¹³C{¹H} NMR (75.42 MHz, C₆D₆, 293K): δ 197.4 (t, J_(C—P)=9.0, Os—NCN),173.2 (t, J_(C—P)=3.6, Os—C), 148.0 (s, C Ph), 137.2 (s, C Bzm), 133.9(s, C Bzm), 128.2 (q, J_(C—F)=270.0, CF₃), 122.0 (s, CH Bzm), 121.7 (s,CH Bzm), 118.9 (q, J_(C—F)=30.8, C—CF₃), 109.8 (s, CH Bzm), 108.7 (s, CHBzm), 102.0 (q, J_(C—F)=4.0 CH Ph), 37.9 (s, CH₃), 30.9 (t, N=24.8,PCH(CH₃)₂), 19.5 (s, PCH(CH₃)₂). ³¹P{¹H} NMR (121.4 MHz, C₆D₆, 293K): δ21.4 (s, doublet under off resonance conditions). ¹⁹F NMR 282 MHz, C₆D₆,293K): δ −60.10 (CF₃). Method (B): A solution of OsH₆(P^(i)Pr₃)₂ (235mg, 0.455 mmol) in DMF (5 mL) was treated with1,3-bis[(1-methyl)benzylimidazolium-3-yl]-5-trifluoromethyl-benzenediiodide (300 mg, 0.455 mmol). The resulting mixture was refluxed for 20min, getting a very dark solution. After cooling at room temperature thesolvent was removed in vacuo, affording a dark residue. The addition of4 mL of toluene caused the precipitation of a brown solid that waswashed with further portions of diethyl ether (2×4 mL). The brown solidwas dissolved in THF (10 mL) and K^(t)BuO (102 mg, 0.906 mmol) wasadded. After stirring for 20 min the resulting suspension was filteredthrough Celite to remove the iodide salts. The solution thus obtainedwas evaporated to dryness and pentane (4 mL) was added to afford anorange solid that was washed with further portions of pentane (1×3 mL)and dried in vacuo. This orange solid was suspended in diethyl ether (10mL) and treated with HBF₄:Et₂O (93 μL, 0.680 mmol) getting a whitesuspension. This solid was decanted, washed with further portions ofdiethyl ether (2×4 mL) and dried in vacuo. Yield: 405 mg (89%) Anal.Calcd. for C₄₁H₆₀BF₇N₄OsP₂: C, 49.00; H, 6.02; N, 5.58. Found: C, 49.21;H, 5.79; N, 5.69. HRMS (electrospray, m/z): calcd for [M]⁺: 919.3857;found: 919.4035. IR (cm⁻¹): ν(Os—H) 2097 (w), ν(BF₄) 1080-1000 (vs). ¹HNMR (300 MHz, CD₃CN, 298K): δ 9.60 (m, 2H, CH bzm), 9.41 (s, 2H, CH Ph),8.96 (m, 2H, CH bzm), 8.80 (m, 4H, CH bzm), 5.57 (s, 6H, CH₃), 2.80 (m,6H, CH_(P)), 1.91 (dvt, 36H, J_(HH)=7.1, N=13.5, CH_(3-P)), −4.70 (t,2H, J_(H—P)=13.5, H_(hyd)); ¹³C{¹H} NMR (75.42 MHz, CD₃CN, 293K): δ189.6 (t, J_(C—P)=7.5, NCN), 169.6 (t, J_(C—P)=5.7, Os—C), 146.7 (s, CPh), 137.4 (s, C Bzm), 132.6 (s, C Bzm), 126.7 (q, J_(C—F)=270, CF₃),126.3 (q, J_(C—F)=28.6, CCF₃), 125.4 (s, CH Bzm), 125.1 (s, CH Bzm),113.2 (s, CH Bzm), 112.3 (s, CH Bzm), 105.6 (q, J_(C—F)=3.9, CH Ph),39.1 (s, CH₃), 29.5 (t, N=13.5, PCH(CH₃)₂), 19.6 (s, PCH(CH₃)₂). ³¹P{¹H}NMR (121.4 MHz, CD₃CN, 293K): δ 5.2 (s). ¹⁹F{¹H} NMR (282 MHz, CD₃CN,293K): δ −60.21 (s, CF₃); −151.7 (broad signal, BF₄)

Preparation of Complex A:

Monohydride (250 mg, 0.294 mmol) and1,3-bis[(1-methyl)benzylimidazolium-3-yl]benzene ditetrafluoroborate(181 mg, 0.353 mmol) were dissolved in 5 mL of DMF and triethyl amine(0.6 mL, 4.4 mmol) was added to the solution. The resulting mixture wasrefluxed for 1.5 h and then it was cooled to room temperature. Thesolvent was evaporated under vacuum to afford a brown residue. Additionof acetonitrile afforded a bright yellow solid that was washed withacetonitrile (1×2 mL) and dried in vacuo. Yield: 153 mg (60%). HRMS(electrospray, m/z): calcd for C₄₄H₃₄N₈Os [M]⁺: 867.2562; found:867.2597. ¹H NMR (300 MHz, C₆D₆, 293K): δ 8.29 (d, J_(H—H)=7.7, 4H, CHPh), 8.18 (d, J_(H—H)=7.9, 4H, CH bzm), 7.81 (t, J_(H—H)=7.7, 2H, CHPh), 7.08 (td, J_(H—H)=7.9, J_(H—H)=1.0, 4H, CH bzm), 6.80 (td,J_(H—H)=7.9, J_(H—H)=1.0, 4H, CH bzm), 6.18 (d, J_(H—H)=7.9, 4H, CHbzm), 2.25 (s, 12H, CH₃). ¹³C{¹H} NMR (75.42 MHz, C₆D₆, 293K): δ 192.6(s, Os—NCN), 171.1 (s, Os—C), 146.8 (s, C Ph), 137.2 (s, C Bzm), 133.4(s, C Bzm), 121.43 (s, CH Bzm), 121.03 (s, CH Bzm), 117.8 (s, CH Ph),109.9 (s, CH Bzm), 109.0 (s, CH Bzm), 106.4 (s, CH Ph), 32.7 (s, CH₃).FIG. 4 shows molecular diagram of Complex A with X-ray diffractionanalysis characterization. The structure has two chemically equivalentbut crystallographically independent molecules in the asymmetric unit.Selected bond lengths (Å) and angles (°): Os(1)-C(10)=2.048(7),2.057(7), Os(1)-C(32)=2.045(7), 2.049(8), Os(1)-C(15)=2.026(8),2.032(8), Os(1)-C(1)=2.042(8), 2.037(7), Os(1)-C(23)=2.049(7), 2.037(8),Os(1)-C(37)=2.043(7), 2.051(8); C(15)-Os(1)-C(1)=149.6(3), 149.9(3),C(23)-Os(1)-C(37)=150.0(3), 150.6(3), C(10)-Os(1)-C(32)=177.8(3),178.6(3).

Preparation of Complex A-CF₃:

Monohydride (250 mg, 0.294 mmol) and1,3-bis[(1-methyl)benzylimidazolium-3-yl]-5-trifluoromethyl-benzeneditetrafluoroborate (170 mg, 0.294 mmol) were dissolved in 5 mL of DMFand triethyl amine (0.6 mL, 4.4 mmol) was added to the solution. Theresulting mixture was refluxed for 1.5 h and then it was cooled to roomtemperature. The solvent was evaporated under vacuum to afford a brownresidue. Addition of acetonitrile afforded a bright yellow solid thatwas washed with acetonitrile (1×2 mL) and dried in vacuo. Yield: 147 mg(53%). HRMS (electrospray, m/z): calcd for C₄₅H₃₃F₃N₈Os [M]⁺: 934.2392;found: 934.2398. ¹H NMR (300 MHz, C₆D₆, 293K): δ 8.75 (s, 2H, CHPh-CF₃), 8.24 (d, J_(H—H)=7.8, 2H, CH Ph), 8.16 (d, J_(H—H)=7.8, 2H, CHbzm), 8.14 (d, J_(H—H)=7.8, 2H, CH bzm), 7.78 (t, J_(H—H)=7.8, 1H, CHPh), 7.08 (t, J_(H—H)=7.8, 2H, CH bzm), 6.99 (t, J_(H—H)=7.8, 2H, CHbzm), 6.81 (t, J_(H—H)=7.9, 2H, CH bzm), 6.78 (t, J_(H—H)=7.9, 2H, CHbzm), 6.21 (d, J_(H—H)=7.8, 2H, CH bzm), 6.14 (d, J_(H—H)=7.8, 2H, CHbzm), 2.22 (s, 6H, CH₃), 2.11 (s, 6H, CH₃). ¹³C{¹H} NMR (100.63 MHz,C₆D₆, 293K): δ 192.4 (s, Os—NCN), 192.1 (s, Os—NCN), 179.0 (s, Os—C),170.1 (s, Os—C), 146.7 (s, C Ph), 146.5 (s, C Ph), 137.2 (s, C Bzm),137.1 (s, C Bzm), 133.4 (s, C Bzm), 133.2 (s, C Bzm), 128.4 (q,J_(C—F)=270.4 Hz, CF₃) 122.0 (s, CH Bzm), 121.8 (s, CH Bzm), 121.7 (s,CH Bzm), 121.4 (s, CH Bzm), 119.0 (q, J_(C—F)=30.7 Hz, CCF₃) 118.5 (s,CH Ph), 110.14 (s, CH Bzm), 110.08 (s, CH Bzm), 109.30 (s, CH Bzm),109.28 (s, CH Bzm), 107.0 (s, CH Ph), 103.1 (q, J_(C—F)=3.8 Hz, CH Ph),32.8 (s, CH₃), 32.7 (s, CH₃). ¹⁹F NMR (282 MHz, C₆D₆, 293K): δ −57.1(CF₃).

According to an aspect of the present disclosure, a method of making anosmium(II) complex having Formula I

L¹-Os-L², wherein L¹ and L² are independently a biscarbene tridentateligand, wherein L¹ and L² can be same or different is disclosed. Themethod comprises: (a) reacting a precursor of ligand L¹ with an osmiumprecursor to form an intermediate product, wherein the osmium precursorhaving the formula OsH_(x)(PR₃)_(y), wherein x is an integer from 2 to 6and y is an integer from 2 to 5, and R is selected from the groupconsisting of aryl, alkyl and cycloalkyl; and (b) reacting a precursorof ligand L² with said intermediate product.

In one embodiment of the method, L¹ and L² are monoanionic ligands. Insome embodiments, L¹ and L² are independently selected from ligandshaving Formula II:

wherein Y¹, Y² and Y³ comprise C or N; wherein R³ and R⁴ may representmono-, or di-substitutions, or no substitution; wherein R⁵ may representmono-, di-, or tri-substitutions, or no substitution; wherein R¹, R²,R³, R⁴ and R⁵ are independently selected from the group consisting ofhydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl,alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester,nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof; wherein any two adjacent substituents of R¹, R²,R³, R⁴ and R⁵ are optionally joined to form a ring; and wherein the dashlines show the connection points to osmium.

In one embodiment of the method, Y¹, Y² and Y³ comprise C. In oneembodiment, Y¹ and Y³ comprise C, and Y² is N. In one embodiment, Y¹ andY³ are N, and Y² comprise C. In one embodiment, R¹ and R² areindependently selected from the group consisting of alkyl, cycloalkyl,aryl, heteroaryl, and partially or fully deuterated variants thereof. Inone embodiment, R¹ and R² are independently selected from the groupconsisting of methyl, ethyl, propyl, 1-methylethyl, butyl,1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fullydeuterated variants thereof, and combinations thereof.

In one embodiment of the method, the osmium precursor having the formulaOsH₆(PR₃)₂. In another embodiment, R in the osmium precursor having theformula OsH_(x)(PR₃)_(y) is selected from the group consisting ofmethyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl,2-methylpropyl, 1,1-dimethylethyl, cyclohexyl, phenyl,2,6-dimethylphenyl, and 2-methylphenyl. In other embodiment, R is1-methylethyl.

In another embodiment, the ligands having Formula II are selected fromthe group consisting of:

According to an embodiment, a compound having a structure according toFormula I, L¹-Os-L² is provided, wherein L¹ and L² are different;wherein L¹ and L² are independently selected from ligands having FormulaII,

In Formula II, Y¹, Y² and Y³ comprise C or N; wherein R³ and R⁴ mayrepresent mono-, or di-substitutions, or no substitution; wherein R⁵ mayrepresent mono-, di-, or tri-substitutions, or no substitution; whereinR¹ and R² are independently selected from the group consisting of alkyland cycloalkyl; wherein R³, R⁴ and R⁵ are independently selected fromthe group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl,aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof;wherein any two adjacent substituents of R¹, R², R³, R⁴ and R⁵ areoptionally joined to condense into a fused ring; and wherein the dashlines show the connection points to osmium.

In an embodiment of the compound, Y¹, Y² and Y³ comprise C. In oneembodiment of the compound, Y¹ and Y³ comprise C, and Y² is N. In someembodiments, Y¹ and Y³ are N, and Y² comprise C. In one embodiment, R¹and R² are independently selected from the group consisting of alkyl,cycloalkyl, aryl, heteroaryl, and partially or fully deuterated variantsthereof. In one embodiment, R¹ and R² are independently selected fromthe group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl,1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fullydeuterated variants thereof, and combinations thereof.

In some embodiments of the compound, L¹ and L² are independentlyselected from ligands having Formula III:

wherein X¹, X², X³, X⁴, X⁵, X⁶, X⁷ and X⁸ comprise C or N. In oneembodiment, X¹, X², X³, X⁴, X⁵, X⁶, X⁷ and X⁸ comprise C.

In some embodiments, the ligands having Formula II are selected from thegroup consisting of: L¹⁰¹ to L¹⁵⁹ defined herein.

In some embodiments, the compound having a structure according toFormula I, L¹-Os-L² is selected from the group consisting of Compounds 1to 1159 defined in Table 1 below:

TABLE 1 Compound Number L¹ L² 1. L¹⁰¹ L¹⁰² 2. L¹⁰¹ L¹⁰³ 3. L¹⁰¹ L¹⁰⁴ 4.L¹⁰¹ L¹⁰⁵ 5. L¹⁰¹ L¹⁰⁶ 6. L¹⁰¹ L¹⁰⁷ 7. L¹⁰¹ L¹⁰⁸ 8. L¹⁰¹ L¹⁰⁹ 9. L¹⁰¹L¹¹⁰ 10. L¹⁰¹ L¹¹¹ 11. L¹⁰¹ L¹¹² 12. L¹⁰¹ L¹¹³ 13. L¹⁰¹ L¹¹⁴ 14. L¹⁰¹L¹¹⁵ 15. L¹⁰¹ L¹¹⁶ 16. L¹⁰¹ L¹¹⁷ 17. L¹⁰¹ L¹¹⁸ 18. L¹⁰¹ L¹¹⁹ 19. L¹⁰¹L¹²⁰ 20. L¹⁰¹ L¹²¹ 21. L¹⁰¹ L¹²² 22. L¹⁰¹ L¹²³ 23. L¹⁰¹ L¹²⁴ 24. L¹⁰¹L¹²⁵ 25. L¹⁰¹ L¹²⁶ 26. L¹⁰¹ L¹²⁷ 27. L¹⁰¹ L¹²⁸ 28. L¹⁰¹ L¹²⁹ 29. L¹⁰¹L¹³⁰ 30. L¹⁰¹ L¹³¹ 31. L¹⁰¹ L¹³² 32. L¹⁰¹ L¹³³ 33. L¹⁰¹ L¹³⁴ 34. L¹⁰¹L¹³⁵ 35. L¹⁰¹ L¹³⁶ 36. L¹⁰¹ L¹³⁷ 37. L¹⁰¹ L¹³⁸ 38. L¹⁰¹ L¹³⁹ 39. L¹⁰¹L¹⁴⁰ 40. L¹⁰¹ L¹⁴¹ 41. L¹⁰¹ L¹⁴² 42. L¹⁰¹ L¹⁴³ 43. L¹⁰¹ L¹⁴⁴ 44. L¹⁰¹L¹⁴⁵ 45. L¹⁰¹ L¹⁴⁶ 46. L¹⁰¹ L¹⁴⁷ 47. L¹⁰¹ L¹⁴⁸ 48. L¹⁰¹ L¹⁴⁹ 49. L¹⁰¹L¹⁵⁰ 50. L¹⁰¹ L¹⁵¹ 51. L¹⁰¹ L¹⁵² 52. L¹⁰¹ L¹⁵³ 53. L¹⁰¹ L¹⁵⁴ 54. L¹⁰¹L¹⁵⁵ 55. L¹⁰¹ L¹⁵⁶ 56. L¹⁰¹ L¹⁵⁷ 57. L¹⁰¹ L¹⁵⁸ 58. L¹⁰¹ L¹⁵⁹ 59. L¹⁰²L¹⁰³ 60. L¹⁰² L¹⁰⁴ 61. L¹⁰² L¹⁰⁵ 62. L¹⁰² L¹⁰⁶ 63. L¹⁰² L¹⁰⁷ 64. L¹⁰²L¹⁰⁸ 65. L¹⁰² L¹⁰⁹ 66. L¹⁰² L¹¹⁰ 67. L¹⁰² L¹¹¹ 68. L¹⁰² L¹¹² 69. L¹⁰²L¹¹³ 70. L¹⁰² L¹¹⁴ 71. L¹⁰² L¹¹⁵ 72. L¹⁰² L¹¹⁶ 73. L¹⁰² L¹¹⁷ 74. L¹⁰²L¹¹⁸ 75. L¹⁰² L¹¹⁹ 76. L¹⁰² L¹²⁰ 77. L¹⁰² L¹²¹ 78. L¹⁰² L¹²² 79. L¹⁰²L¹²³ 80. L¹⁰² L¹²⁴ 81. L¹⁰² L¹²⁵ 82. L¹⁰² L¹²⁶ 83. L¹⁰² L¹²⁷ 84. L¹⁰²L¹²⁸ 85. L¹⁰² L¹²⁹ 86. L¹⁰² L¹³⁰ 87. L¹⁰² L¹³¹ 88. L¹⁰² L¹³² 89. L¹⁰²L¹³³ 90. L¹⁰² L¹³⁴ 91. L¹⁰² L¹³⁵ 92. L¹⁰² L¹³⁶ 93. L¹⁰² L¹³⁷ 94. L¹⁰²L¹³⁸ 95. L¹⁰² L¹³⁹ 96. L¹⁰² L¹⁴⁰ 97. L¹⁰² L¹⁴¹ 98. L¹⁰² L¹⁴² 99. L¹⁰²L¹⁴³ 100. L¹⁰² L¹⁴⁴ 101. L¹⁰² L¹⁴⁵ 102. L¹⁰² L¹⁴⁶ 103. L¹⁰² L¹⁴⁷ 104.L¹⁰² L¹⁴⁸ 105. L¹⁰² L¹⁴⁹ 106. L¹⁰² L¹⁵⁰ 107. L¹⁰² L¹⁵¹ 108. L¹⁰² L¹⁵²109. L¹⁰² L¹⁵³ 110. L¹⁰² L¹⁵⁴ 111. L¹⁰² L¹⁵⁵ 112. L¹⁰² L¹⁵⁶ 113. L¹⁰²L¹⁵⁷ 114. L¹⁰² L¹⁵⁸ 115. L¹⁰² L¹⁵⁹ 116. L¹⁰³ L¹⁰⁴ 117. L¹⁰³ L¹⁰⁵ 118.L¹⁰³ L¹⁰⁶ 119. L¹⁰³ L¹⁰⁷ 120. L¹⁰³ L¹⁰⁸ 121. L¹⁰³ L¹⁰⁹ 122. L¹⁰³ L¹¹⁰123. L¹⁰³ L¹¹¹ 124. L¹⁰³ L¹¹² 125. L¹⁰³ L¹¹³ 126. L¹⁰³ L¹¹⁴ 127. L¹⁰³L¹¹⁵ 128. L¹⁰³ L¹¹⁶ 129. L¹⁰³ L¹¹⁷ 130. L¹⁰³ L¹¹⁸ 131. L¹⁰³ L¹¹⁹ 132.L¹⁰³ L¹²⁰ 133. L¹⁰³ L¹²¹ 134. L¹⁰³ L¹²² 135. L¹⁰³ L¹²³ 136. L¹⁰³ L¹²⁴137. L¹⁰³ L¹²⁵ 138. L¹⁰³ L¹²⁶ 139. L¹⁰³ L¹²⁷ 140. L¹⁰³ L¹²⁸ 141. L¹⁰³L¹²⁹ 142. L¹⁰³ L¹³⁰ 143. L¹⁰³ L¹³¹ 144. L¹⁰³ L¹³² 145. L¹⁰³ L¹³³ 146.L¹⁰³ L¹³⁴ 147. L¹⁰³ L¹³⁵ 148. L¹⁰³ L¹³⁶ 149. L¹⁰³ L¹³⁷ 150. L¹⁰³ L¹³⁸151. L¹⁰³ L¹³⁹ 152. L¹⁰³ L¹⁴⁰ 153. L¹⁰³ L¹⁴¹ 154. L¹⁰³ L¹⁴² 155. L¹⁰³L¹⁴³ 156. L¹⁰³ L¹⁴⁴ 157. L¹⁰³ L¹⁴⁵ 158. L¹⁰³ L¹⁴⁶ 159. L¹⁰³ L¹⁴⁷ 160.L¹⁰³ L¹⁴⁸ 161. L¹⁰³ L¹⁴⁹ 162. L¹⁰³ L¹⁵⁰ 163. L¹⁰³ L¹⁵¹ 164. L¹⁰³ L¹⁵²165. L¹⁰³ L¹⁵³ 166. L¹⁰³ L¹⁵⁴ 167. L¹⁰³ L¹⁵⁵ 168. L¹⁰³ L¹⁵⁶ 169. L¹⁰³L¹⁵⁷ 170. L¹⁰³ L¹⁵⁸ 171. L¹⁰³ L¹⁵⁹ 172. L¹⁰⁴ L¹⁰⁵ 173. L¹⁰⁴ L¹⁰⁶ 174.L¹⁰⁴ L¹⁰⁷ 175. L¹⁰⁴ L¹⁰⁸ 176. L¹⁰⁴ L¹⁰⁹ 177. L¹⁰⁴ L¹¹⁰ 178. L¹⁰⁴ L¹¹¹179. L¹⁰⁴ L¹¹² 180. L¹⁰⁴ L¹¹³ 181. L¹⁰⁴ L¹¹⁴ 182. L¹⁰⁴ L¹¹⁵ 183. L¹⁰⁴L¹¹⁶ 184. L¹⁰⁴ L¹¹⁷ 185. L¹⁰⁴ L¹¹⁸ 186. L¹⁰⁴ L¹¹⁹ 187. L¹⁰⁴ L¹²⁰ 188.L¹⁰⁴ L¹²¹ 189. L¹⁰⁴ L¹²² 190. L¹⁰⁴ L¹²³ 191. L¹⁰⁴ L¹²⁴ 192. L¹⁰⁴ L¹²⁵193. L¹⁰⁴ L¹²⁶ 194. L¹⁰⁴ L¹²⁷ 195. L¹⁰⁴ L¹²⁸ 196. L¹⁰⁴ L¹²⁹ 197. L¹⁰⁴L¹³⁰ 198. L¹⁰⁴ L¹³¹ 199. L¹⁰⁴ L¹³² 200. L¹⁰⁴ L¹³³ 201. L¹⁰⁴ L¹³⁴ 202.L¹⁰⁴ L¹³⁵ 203. L¹⁰⁴ L¹³⁶ 204. L¹⁰⁴ L¹³⁷ 205. L¹⁰⁴ L¹³⁸ 206. L¹⁰⁴ L¹³⁹207. L¹⁰⁴ L¹⁴⁰ 208. L¹⁰⁴ L¹⁴¹ 209. L¹⁰⁴ L¹⁴² 210. L¹⁰⁴ L¹⁴³ 211. L¹⁰⁴L¹⁴⁴ 212. L¹⁰⁴ L¹⁴⁵ 213. L¹⁰⁴ L¹⁴⁶ 214. L¹⁰⁴ L¹⁴⁷ 215. L¹⁰⁴ L¹⁴⁸ 216.L¹⁰⁴ L¹⁴⁹ 217. L¹⁰⁴ L¹⁵⁰ 218. L¹⁰⁴ L¹⁵¹ 219. L¹⁰⁴ L¹⁵² 220. L¹⁰⁴ L¹⁵³221. L¹⁰⁴ L¹⁵⁴ 222. L¹⁰⁴ L¹⁵⁵ 223. L¹⁰⁴ L¹⁵⁶ 224. L¹⁰⁴ L¹⁵⁷ 225. L¹⁰⁴L¹⁵⁸ 226. L¹⁰⁴ L¹⁵⁹ 227. L¹⁰⁵ L¹⁰⁶ 228. L¹⁰⁵ L¹⁰⁷ 229. L¹⁰⁵ L¹⁰⁸ 230.L¹⁰⁵ L¹⁰⁹ 231. L¹⁰⁵ L¹¹⁰ 232. L¹⁰⁵ L¹¹¹ 233. L¹⁰⁵ L¹¹² 234. L¹⁰⁵ L¹¹³235. L¹⁰⁵ L¹¹⁴ 236. L¹⁰⁵ L¹¹⁵ 237. L¹⁰⁵ L¹¹⁶ 238. L¹⁰⁵ L¹¹⁷ 239. L¹⁰⁵L¹¹⁸ 240. L¹⁰⁵ L¹¹⁹ 241. L¹⁰⁵ L¹²⁰ 242. L¹⁰⁵ L¹²¹ 243. L¹⁰⁵ L¹²² 244.L¹⁰⁵ L¹²³ 245. L¹⁰⁵ L¹²⁴ 246. L¹⁰⁵ L¹²⁵ 247. L¹⁰⁵ L¹²⁶ 248. L¹⁰⁵ L¹²⁷249. L¹⁰⁵ L¹²⁸ 250. L¹⁰⁵ L¹²⁹ 251. L¹⁰⁵ L¹³⁰ 252. L¹⁰⁵ L¹³¹ 253. L¹⁰⁵L¹³² 254. L¹⁰⁵ L¹³³ 255. L¹⁰⁵ L¹³⁴ 256. L¹⁰⁵ L¹³⁵ 257. L¹⁰⁵ L¹³⁶ 258.L¹⁰⁵ L¹³⁷ 259. L¹⁰⁵ L¹³⁸ 260. L¹⁰⁵ L¹³⁹ 261. L¹⁰⁵ L¹⁴⁰ 262. L¹⁰⁵ L¹⁴¹263. L¹⁰⁵ L¹⁴² 264. L¹⁰⁵ L¹⁴³ 265. L¹⁰⁵ L¹⁴⁴ 266. L¹⁰⁵ L¹⁴⁵ 267. L¹⁰⁵L¹⁴⁶ 268. L¹⁰⁵ L¹⁴⁷ 269. L¹⁰⁵ L¹⁴⁸ 270. L¹⁰⁵ L¹⁴⁹ 271. L¹⁰⁵ L¹⁵⁰ 272.L¹⁰⁵ L¹⁵¹ 273. L¹⁰⁵ L¹⁵² 274. L¹⁰⁵ L¹⁵³ 275. L¹⁰⁵ L¹⁵⁴ 276. L¹⁰⁵ L¹⁵⁵277. L¹⁰⁵ L¹⁵⁶ 278. L¹⁰⁵ L¹⁵⁷ 279. L¹⁰⁵ L¹⁵⁸ 280. L¹⁰⁵ L¹⁵⁹ 281. L¹⁰⁶L¹⁰⁷ 282. L¹⁰⁶ L¹⁰⁸ 283. L¹⁰⁶ L¹⁰⁹ 284. L¹⁰⁶ L¹¹⁰ 285. L¹⁰⁶ L¹¹¹ 286.L¹⁰⁶ L¹¹² 287. L¹⁰⁶ L¹¹³ 288. L¹⁰⁶ L¹¹⁴ 289. L¹⁰⁶ L¹¹⁵ 290. L¹⁰⁶ L¹¹⁶291. L¹⁰⁶ L¹¹⁷ 292. L¹⁰⁶ L¹¹⁸ 293. L¹⁰⁶ L¹¹⁹ 294. L¹⁰⁶ L¹²⁰ 295. L¹⁰⁶L¹²¹ 296. L¹⁰⁶ L¹²² 297. L¹⁰⁶ L¹²³ 298. L¹⁰⁶ L¹²⁴ 299. L¹⁰⁶ L¹²⁵ 300.L¹⁰⁶ L¹²⁶ 301. L¹⁰⁶ L¹²⁷ 302. L¹⁰⁶ L¹²⁸ 303. L¹⁰⁶ L¹²⁹ 304. L¹⁰⁶ L¹³⁰305. L¹⁰⁶ L¹³¹ 306. L¹⁰⁶ L¹³² 307. L¹⁰⁶ L¹³³ 308. L¹⁰⁶ L¹³⁴ 309. L¹⁰⁶L¹³⁵ 310. L¹⁰⁶ L¹³⁶ 311. L¹⁰⁶ L¹³⁷ 312. L¹⁰⁶ L¹³⁸ 313. L¹⁰⁶ L¹³⁹ 314.L¹⁰⁶ L¹⁴⁰ 315. L¹⁰⁶ L¹⁴¹ 316. L¹⁰⁶ L¹⁴² 317. L¹⁰⁶ L¹⁴³ 318. L¹⁰⁶ L¹⁴⁴319. L¹⁰⁶ L¹⁴⁵ 320. L¹⁰⁶ L¹⁴⁶ 321. L¹⁰⁶ L¹⁴⁷ 322. L¹⁰⁶ L¹⁴⁸ 323. L¹⁰⁶L¹⁴⁹ 324. L¹⁰⁶ L¹⁵⁰ 325. L¹⁰⁶ L¹⁵¹ 326. L¹⁰⁶ L¹⁵² 327. L¹⁰⁶ L¹⁵³ 328.L¹⁰⁶ L¹⁵⁴ 329. L¹⁰⁶ L¹⁵⁵ 330. L¹⁰⁶ L¹⁵⁶ 331. L¹⁰⁶ L¹⁵⁷ 332. L¹⁰⁶ L¹⁵⁸333. L¹⁰⁶ L¹⁵⁹ 334. L¹⁰⁷ L¹⁰⁸ 335. L¹⁰⁷ L¹⁰⁹ 336. L¹⁰⁷ L¹¹⁰ 337. L¹⁰⁷L¹¹¹ 338. L¹⁰⁷ L¹¹² 339. L¹⁰⁷ L¹¹³ 340. L¹⁰⁷ L¹¹⁴ 341. L¹⁰⁷ L¹¹⁵ 342.L¹⁰⁷ L¹¹⁶ 343. L¹⁰⁷ L¹¹⁷ 344. L¹⁰⁷ L¹¹⁸ 345. L¹⁰⁷ L¹¹⁹ 346. L¹⁰⁷ L¹²⁰347. L¹⁰⁷ L¹²¹ 348. L¹⁰⁷ L¹²² 349. L¹⁰⁷ L¹²³ 350. L¹⁰⁷ L¹²⁴ 351. L¹⁰⁷L¹²⁵ 352. L¹⁰⁷ L¹²⁶ 353. L¹⁰⁷ L¹²⁷ 354. L¹⁰⁷ L¹²⁸ 355. L¹⁰⁷ L¹²⁹ 356.L¹⁰⁷ L¹³⁰ 357. L¹⁰⁷ L¹³¹ 358. L¹⁰⁷ L¹³² 359. L¹⁰⁷ L¹³³ 360. L¹⁰⁷ L¹³⁴361. L¹⁰⁷ L¹³⁵ 362. L¹⁰⁷ L¹³⁶ 363. L¹⁰⁷ L¹³⁷ 364. L¹⁰⁷ L¹³⁸ 365. L¹⁰⁷L¹³⁹ 366. L¹⁰⁷ L¹⁴⁰ 367. L¹⁰⁷ L¹⁴¹ 368. L¹⁰⁷ L¹⁴² 369. L¹⁰⁷ L¹⁴³ 370.L¹⁰⁷ L¹⁴⁴ 371. L¹⁰⁷ L¹⁴⁵ 372. L¹⁰⁷ L¹⁴⁶ 373. L¹⁰⁷ L¹⁴⁷ 374. L¹⁰⁷ L¹⁴⁸375. L¹⁰⁷ L¹⁴⁹ 376. L¹⁰⁷ L¹⁵⁰ 377. L¹⁰⁷ L¹⁵¹ 378. L¹⁰⁷ L¹⁵² 379. L¹⁰⁷L¹⁵³ 380. L¹⁰⁷ L¹⁵⁴ 381. L¹⁰⁷ L¹⁵⁵ 382. L¹⁰⁷ L¹⁵⁶ 383. L¹⁰⁷ L¹⁵⁷ 384.L¹⁰⁷ L¹⁵⁸ 385. L¹⁰⁷ L¹⁵⁹ 386. L¹⁰⁸ L¹⁰⁹ 387. L¹⁰⁸ L¹¹⁰ 388. L¹⁰⁸ L¹¹¹389. L¹⁰⁸ L¹¹² 390. L¹⁰⁸ L¹¹³ 391. L¹⁰⁸ L¹¹⁴ 392. L¹⁰⁸ L¹¹⁵ 393. L¹⁰⁸L¹¹⁶ 394. L¹⁰⁸ L¹¹⁷ 395. L¹⁰⁸ L¹¹⁸ 396. L¹⁰⁸ L¹¹⁹ 397. L¹⁰⁸ L¹²⁰ 398.L¹⁰⁸ L¹²¹ 399. L¹⁰⁸ L¹²² 400. L¹⁰⁸ L¹²³ 401. L¹⁰⁸ L¹²⁴ 402. L¹⁰⁸ L¹²⁵403. L¹⁰⁸ L¹²⁶ 404. L¹⁰⁸ L¹²⁷ 405. L¹⁰⁸ L¹²⁸ 406. L¹⁰⁸ L¹²⁹ 407. L¹⁰⁸L¹³⁰ 408. L¹⁰⁸ L¹³¹ 409. L¹⁰⁸ L¹³² 410. L¹⁰⁸ L¹³³ 411. L¹⁰⁸ L¹³⁴ 412.L¹⁰⁸ L¹³⁵ 413. L¹⁰⁸ L¹³⁶ 414. L¹⁰⁸ L¹³⁷ 415. L¹⁰⁸ L¹³⁸ 416. L¹⁰⁸ L¹³⁹417. L¹⁰⁸ L¹⁴⁰ 418. L¹⁰⁸ L¹⁴¹ 419. L¹⁰⁸ L¹⁴² 420. L¹⁰⁸ L¹⁴³ 421. L¹⁰⁸L¹⁴⁴ 422. L¹⁰⁸ L¹⁴⁵ 423. L¹⁰⁸ L¹⁴⁶ 424. L¹⁰⁸ L¹⁴⁷ 425. L¹⁰⁸ L¹⁴⁸ 426.L¹⁰⁸ L¹⁴⁹ 427. L¹⁰⁸ L¹⁵⁰ 428. L¹⁰⁸ L¹⁵¹ 429. L¹⁰⁸ L¹⁵² 430. L¹⁰⁸ L¹⁵³431. L¹⁰⁸ L¹⁵⁴ 432. L¹⁰⁸ L¹⁵⁵ 433. L¹⁰⁸ L¹⁵⁶ 434. L¹⁰⁸ L¹⁵⁷ 435. L¹⁰⁸L¹⁵⁸ 436. L¹⁰⁸ L¹⁵⁹ 437. L¹⁰⁹ L¹¹⁰ 438. L¹⁰⁹ L¹¹¹ 439. L¹⁰⁹ L¹¹² 440.L¹⁰⁹ L¹¹³ 441. L¹⁰⁹ L¹¹⁴ 442. L¹⁰⁹ L¹¹⁵ 443. L¹⁰⁹ L¹¹⁶ 444. L¹⁰⁹ L¹¹⁷445. L¹⁰⁹ L¹¹⁸ 446. L¹⁰⁹ L¹¹⁹ 447. L¹⁰⁹ L¹²⁰ 448. L¹⁰⁹ L¹²¹ 449. L¹⁰⁹L¹²² 450. L¹⁰⁹ L¹²³ 451. L¹⁰⁹ L¹²⁴ 452. L¹⁰⁹ L¹²⁵ 453. L¹⁰⁹ L¹²⁶ 454.L¹⁰⁹ L¹²⁷ 455. L¹⁰⁹ L¹²⁸ 456. L¹⁰⁹ L¹²⁹ 457. L¹⁰⁹ L¹³⁰ 458. L¹⁰⁹ L¹³¹459. L¹⁰⁹ L¹³² 460. L¹⁰⁹ L¹³³ 461. L¹⁰⁹ L¹³⁴ 462. L¹⁰⁹ L¹³⁵ 463. L¹⁰⁹L¹³⁶ 464. L¹⁰⁹ L¹³⁷ 465. L¹⁰⁹ L¹³⁸ 466. L¹⁰⁹ L¹³⁹ 467. L¹⁰⁹ L¹⁴⁰ 468.L¹⁰⁹ L¹⁴¹ 469. L¹⁰⁹ L¹⁴² 470. L¹⁰⁹ L¹⁴³ 471. L¹⁰⁹ L¹⁴⁴ 472. L¹⁰⁹ L¹⁴⁵473. L¹⁰⁹ L¹⁴⁶ 474. L¹⁰⁹ L¹⁴⁷ 475. L¹⁰⁹ L¹⁴⁸ 476. L¹⁰⁹ L¹⁴⁹ 477. L¹⁰⁹L¹⁵⁰ 478. L¹⁰⁹ L¹⁵¹ 479. L¹⁰⁹ L¹⁵² 480. L¹⁰⁹ L¹⁵³ 481. L¹⁰⁹ L¹⁵⁴ 482.L¹⁰⁹ L¹⁵⁵ 483. L¹⁰⁹ L¹⁵⁶ 484. L¹⁰⁹ L¹⁵⁷ 485. L¹⁰⁹ L¹⁵⁸ 486. L¹⁰⁹ L¹⁵⁹487. L¹¹⁰ L¹¹¹ 488. L¹¹⁰ L¹¹² 489. L¹¹⁰ L¹¹³ 490. L¹¹⁰ L¹¹⁴ 491. L¹¹⁰L¹¹⁵ 492. L¹¹⁰ L¹¹⁶ 493. L¹¹⁰ L¹¹⁷ 494. L¹¹⁰ L¹¹⁸ 495. L¹¹⁰ L¹¹⁹ 496.L¹¹⁰ L¹²⁰ 497. L¹¹⁰ L¹²¹ 498. L¹¹⁰ L¹²² 499. L¹¹⁰ L¹²³ 500. L¹¹⁰ L¹²⁴501. L¹¹⁰ L¹²⁵ 502. L¹¹⁰ L¹²⁶ 503. L¹¹⁰ L¹²⁷ 504. L¹¹⁰ L¹²⁸ 505. L¹¹⁰L¹²⁹ 506. L¹¹⁰ L¹³⁰ 507. L¹¹⁰ L¹³¹ 508. L¹¹⁰ L¹³² 509. L¹¹⁰ L¹³³ 510.L¹¹⁰ L¹³⁴ 511. L¹¹⁰ L¹³⁵ 512. L¹¹⁰ L¹³⁶ 513. L¹¹⁰ L¹³⁷ 514. L¹¹⁰ L¹³⁸515. L¹¹⁰ L¹³⁹ 516. L¹¹⁰ L¹⁴⁰ 517. L¹¹⁰ L¹⁴¹ 518. L¹¹⁰ L¹⁴² 519. L¹¹⁰L¹⁴³ 520. L¹¹⁰ L¹⁴⁴ 521. L¹¹⁰ L¹⁴⁵ 522. L¹¹⁰ L¹⁴⁶ 523. L¹¹⁰ L¹⁴⁷ 524.L¹¹⁰ L¹⁴⁸ 525. L¹¹⁰ L¹⁴⁹ 526. L¹¹⁰ L¹⁵⁰ 527. L¹¹⁰ L¹⁵¹ 528. L¹¹⁰ L¹⁵²529. L¹¹⁰ L¹⁵³ 530. L¹¹⁰ L¹⁵⁴ 531. L¹¹⁰ L¹⁵⁵ 532. L¹¹⁰ L¹⁵⁶ 533. L¹¹⁰L¹⁵⁷ 534. L¹¹⁰ L¹⁵⁸ 535. L¹¹⁰ L¹⁵⁹ 536. L¹¹¹ L¹¹² 537. L¹¹¹ L¹¹³ 538.L¹¹¹ L¹¹⁴ 539. L¹¹¹ L¹¹⁵ 540. L¹¹¹ L¹¹⁶ 541. L¹¹¹ L¹¹⁷ 542. L¹¹¹ L¹¹⁸543. L¹¹¹ L¹¹⁹ 544. L¹¹¹ L¹²⁰ 545. L¹¹¹ L¹²¹ 546. L¹¹¹ L¹²² 547. L¹¹¹L¹²³ 548. L¹¹¹ L¹²⁴ 549. L¹¹¹ L¹²⁵ 550. L¹¹¹ L¹²⁶ 551. L¹¹¹ L¹²⁷ 552.L¹¹¹ L¹²⁸ 553. L¹¹¹ L¹²⁹ 554. L¹¹¹ L¹³⁰ 555. L¹¹¹ L¹³¹ 556. L¹¹¹ L¹³²557. L¹¹¹ L¹³³ 558. L¹¹¹ L¹³⁴ 559. L¹¹¹ L¹³⁵ 560. L¹¹¹ L¹³⁶ 561. L¹¹¹L¹³⁷ 562. L¹¹¹ L¹³⁸ 563. L¹¹¹ L¹³⁹ 564. L¹¹¹ L¹⁴⁰ 565. L¹¹¹ L¹⁴¹ 566.L¹¹¹ L¹⁴² 567. L¹¹¹ L¹⁴³ 568. L¹¹¹ L¹⁴⁴ 569. L¹¹¹ L¹⁴⁵ 570. L¹¹¹ L¹⁴⁶571. L¹¹¹ L¹⁴⁷ 572. L¹¹¹ L¹⁴⁸ 573. L¹¹¹ L¹⁴⁹ 574. L¹¹¹ L¹⁵⁰ 575. L¹¹¹L¹⁵¹ 576. L¹¹¹ L¹⁵² 577. L¹¹¹ L¹⁵³ 578. L¹¹¹ L¹⁵⁴ 579. L¹¹¹ L¹⁵⁵ 580.L¹¹¹ L¹⁵⁶ 581. L¹¹¹ L¹⁵⁷ 582. L¹¹¹ L¹⁵⁸ 583. L¹¹¹ L¹⁵⁹ 584. L¹¹² L¹¹³585. L¹¹² L¹¹⁴ 586. L¹¹² L¹¹⁵ 587. L¹¹² L¹¹⁶ 588. L¹¹² L¹¹⁷ 589. L¹¹²L¹¹⁸ 590. L¹¹² L¹¹⁹ 591. L¹¹² L¹²⁰ 592. L¹¹² L¹²¹ 593. L¹¹² L¹²² 594.L¹¹² L¹²³ 595. L¹¹² L¹²⁴ 596. L¹¹² L¹²⁵ 597. L¹¹² L¹²⁶ 598. L¹¹² L¹²⁷599. L¹¹² L¹²⁸ 600. L¹¹² L¹²⁹ 601. L¹¹² L¹³⁰ 602. L¹¹² L¹³¹ 603. L¹¹²L¹³² 604. L¹¹² L¹³³ 605. L¹¹² L¹³⁴ 606. L¹¹² L¹³⁵ 607. L¹¹² L¹³⁶ 608.L¹¹² L¹³⁷ 609. L¹¹² L¹³⁸ 610. L¹¹² L¹³⁹ 611. L¹¹² L¹⁴⁰ 612. L¹¹² L¹⁴¹613. L¹¹² L¹⁴² 614. L¹¹² L¹⁴³ 615. L¹¹² L¹⁴⁴ 616. L¹¹² L¹⁴⁵ 617. L¹¹²L¹⁴⁶ 618. L¹¹² L¹⁴⁷ 619. L¹¹² L¹⁴⁸ 620. L¹¹² L¹⁴⁹ 621. L¹¹² L¹⁵⁰ 622.L¹¹² L¹⁵¹ 623. L¹¹² L¹⁵² 624. L¹¹² L¹⁵³ 625. L¹¹² L¹⁵⁴ 626. L¹¹² L¹⁵⁵627. L¹¹² L¹⁵⁶ 628. L¹¹² L¹⁵⁷ 629. L¹¹² L¹⁵⁸ 630. L¹¹² L¹⁵⁹ 631. L¹¹³L¹¹⁴ 632. L¹¹³ L¹¹⁵ 633. L¹¹³ L¹¹⁶ 634. L¹¹³ L¹¹⁷ 635. L¹¹³ L¹¹⁸ 636.L¹¹³ L¹¹⁹ 637. L¹¹³ L¹²⁰ 638. L¹¹³ L¹²¹ 639. L¹¹³ L¹²² 640. L¹¹³ L¹²³641. L¹¹³ L¹²⁴ 642. L¹¹³ L¹²⁵ 643. L¹¹³ L¹²⁶ 644. L¹¹³ L¹²⁷ 645. L¹¹³L¹²⁸ 646. L¹¹³ L¹²⁹ 647. L¹¹³ L¹³⁰ 648. L¹¹³ L¹³¹ 649. L¹¹³ L¹³² 650.L¹¹³ L¹³³ 651. L¹¹³ L¹³⁴ 652. L¹¹³ L¹³⁵ 653. L¹¹³ L¹³⁶ 654. L¹¹³ L¹³⁷655. L¹¹³ L¹³⁸ 656. L¹¹³ L¹³⁹ 657. L¹¹³ L¹⁴⁰ 658. L¹¹³ L¹⁴¹ 659. L¹¹³L¹⁴² 660. L¹¹³ L¹⁴³ 661. L¹¹³ L¹⁴⁴ 662. L¹¹³ L¹⁴⁵ 663. L¹¹³ L¹⁴⁶ 664.L¹¹³ L¹⁴⁷ 665. L¹¹³ L¹⁴⁸ 666. L¹¹³ L¹⁴⁹ 667. L¹¹³ L¹⁵⁰ 668. L¹¹³ L¹⁵¹669. L¹¹³ L¹⁵² 670. L¹¹³ L¹⁵³ 671. L¹¹³ L¹⁵⁴ 672. L¹¹³ L¹⁵⁵ 673. L¹¹³L¹⁵⁶ 674. L¹¹³ L¹⁵⁷ 675. L¹¹³ L¹⁵⁸ 676. L¹¹³ L¹⁵⁹ 677. L¹¹⁴ L¹¹⁵ 678.L¹¹⁴ L¹¹⁶ 679. L¹¹⁴ L¹¹⁷ 680. L¹¹⁴ L¹¹⁸ 681. L¹¹⁴ L¹¹⁹ 682. L¹¹⁴ L¹²⁰683. L¹¹⁴ L¹²¹ 684. L¹¹⁴ L¹²² 685. L¹¹⁴ L¹²³ 686. L¹¹⁴ L¹²⁴ 687. L¹¹⁴L¹²⁵ 688. L¹¹⁴ L¹²⁶ 689. L¹¹⁴ L¹²⁷ 690. L¹¹⁴ L¹²⁸ 691. L¹¹⁴ L¹²⁹ 692.L¹¹⁴ L¹³⁰ 693. L¹¹⁴ L¹³¹ 694. L¹¹⁴ L¹³² 695. L¹¹⁴ L¹³³ 696. L¹¹⁴ L¹³⁴697. L¹¹⁴ L¹³⁵ 698. L¹¹⁴ L¹³⁶ 699. L¹¹⁴ L¹³⁷ 700. L¹¹⁴ L¹³⁸ 701. L¹¹⁴L¹³⁹ 702. L¹¹⁴ L¹⁴⁰ 703. L¹¹⁴ L¹⁴¹ 704. L¹¹⁴ L¹⁴² 705. L¹¹⁴ L¹⁴³ 706.L¹¹⁴ L¹⁴⁴ 707. L¹¹⁴ L¹⁴⁵ 708. L¹¹⁴ L¹⁴⁶ 709. L¹¹⁴ L¹⁴⁷ 710. L¹¹⁴ L¹⁴⁸711. L¹¹⁴ L¹⁴⁹ 712. L¹¹⁴ L¹⁵⁰ 713. L¹¹⁴ L¹⁵¹ 714. L¹¹⁴ L¹⁵² 715. L¹¹⁴L¹⁵³ 716. L¹¹⁴ L¹⁵⁴ 717. L¹¹⁴ L¹⁵⁵ 718. L¹¹⁴ L¹⁵⁶ 719. L¹¹⁴ L¹⁵⁷ 720.L¹¹⁴ L¹⁵⁸ 721. L¹¹⁴ L¹⁵⁹ 722. L¹¹⁵ L¹¹⁶ 723. L¹¹⁵ L¹¹⁷ 724. L¹¹⁵ L¹¹⁸725. L¹¹⁵ L¹¹⁹ 726. L¹¹⁵ L¹²⁰ 727. L¹¹⁵ L¹²¹ 728. L¹¹⁵ L¹²² 729. L¹¹⁵L¹²³ 730. L¹¹⁵ L¹²⁴ 731. L¹¹⁵ L¹²⁵ 732. L¹¹⁵ L¹²⁶ 733. L¹¹⁵ L¹²⁷ 734.L¹¹⁵ L¹²⁸ 735. L¹¹⁵ L¹²⁹ 736. L¹¹⁵ L¹³⁰ 737. L¹¹⁵ L¹³¹ 738. L¹¹⁵ L¹³²739. L¹¹⁵ L¹³³ 740. L¹¹⁵ L¹³⁴ 741. L¹¹⁵ L¹³⁵ 742. L¹¹⁵ L¹³⁶ 743. L¹¹⁵L¹³⁷ 744. L¹¹⁵ L¹³⁸ 745. L¹¹⁵ L¹³⁹ 746. L¹¹⁵ L¹⁴⁰ 747. L¹¹⁵ L¹⁴¹ 748.L¹¹⁵ L¹⁴² 749. L¹¹⁵ L¹⁴³ 750. L¹¹⁵ L¹⁴⁴ 751. L¹¹⁵ L¹⁴⁵ 752. L¹¹⁵ L¹⁴⁶753. L¹¹⁵ L¹⁴⁷ 754. L¹¹⁵ L¹⁴⁸ 755. L¹¹⁵ L¹⁴⁹ 756. L¹¹⁵ L¹⁵⁰ 757. L¹¹⁵L¹⁵¹ 758. L¹¹⁵ L¹⁵² 759. L¹¹⁵ L¹⁵³ 760. L¹¹⁵ L¹⁵⁴ 761. L¹¹⁵ L¹⁵⁵ 762.L¹¹⁵ L¹⁵⁶ 763. L¹¹⁵ L¹⁵⁷ 764. L¹¹⁵ L¹⁵⁸ 765. L¹¹⁵ L¹⁵⁹ 766. L¹¹⁶ L¹¹⁷767. L¹¹⁶ L¹¹⁸ 768. L¹¹⁶ L¹¹⁹ 769. L¹¹⁶ L¹²⁰ 770. L¹¹⁶ L¹²¹ 771. L¹¹⁶L¹²² 772. L¹¹⁶ L¹²³ 773. L¹¹⁶ L¹²⁴ 774. L¹¹⁶ L¹²⁵ 775. L¹¹⁶ L¹²⁶ 776.L¹¹⁶ L¹²⁷ 777. L¹¹⁶ L¹²⁸ 778. L¹¹⁶ L¹²⁹ 779. L¹¹⁶ L¹³⁰ 780. L¹¹⁶ L¹³¹781. L¹¹⁶ L¹³² 782. L¹¹⁶ L¹³³ 783. L¹¹⁶ L¹³⁴ 784. L¹¹⁶ L¹³⁵ 785. L¹¹⁶L¹³⁶ 786. L¹¹⁶ L¹³⁷ 787. L¹¹⁶ L¹³⁸ 788. L¹¹⁶ L¹³⁹ 789. L¹¹⁶ L¹⁴⁰ 790.L¹¹⁶ L¹⁴¹ 791. L¹¹⁶ L¹⁴² 792. L¹¹⁶ L¹⁴³ 793. L¹¹⁶ L¹⁴⁴ 794. L¹¹⁶ L¹⁴⁵795. L¹¹⁶ L¹⁴⁶ 796. L¹¹⁶ L¹⁴⁷ 797. L¹¹⁶ L¹⁴⁸ 798. L¹¹⁶ L¹⁴⁹ 799. L¹¹⁶L¹⁵⁰ 800. L¹¹⁶ L¹⁵¹ 801. L¹¹⁶ L¹⁵² 802. L¹¹⁶ L¹⁵³ 803. L¹¹⁶ L¹⁵⁴ 804.L¹¹⁶ L¹⁵⁵ 805. L¹¹⁶ L¹⁵⁶ 806. L¹¹⁶ L¹⁵⁷ 807. L¹¹⁶ L¹⁵⁸ 808. L¹¹⁶ L¹⁵⁹809. L¹¹⁷ L¹¹⁸ 810. L¹¹⁷ L¹¹⁹ 811. L¹¹⁷ L¹²⁰ 812. L¹¹⁷ L¹²¹ 813. L¹¹⁷L¹²² 814. L¹¹⁷ L¹²³ 815. L¹¹⁷ L¹²⁴ 816. L¹¹⁷ L¹²⁵ 817. L¹¹⁷ L¹²⁶ 818.L¹¹⁷ L¹²⁷ 819. L¹¹⁷ L¹²⁸ 820. L¹¹⁷ L¹²⁹ 821. L¹¹⁷ L¹³⁰ 822. L¹¹⁷ L¹³¹823. L¹¹⁷ L¹³² 824. L¹¹⁷ L¹³³ 825. L¹¹⁷ L¹³⁴ 826. L¹¹⁷ L¹³⁵ 827. L¹¹⁷L¹³⁶ 828. L¹¹⁷ L¹³⁷ 829. L¹¹⁷ L¹³⁸ 830. L¹¹⁷ L¹³⁹ 831. L¹¹⁷ L¹⁴⁰ 832.L¹¹⁷ L¹⁴¹ 833. L¹¹⁷ L¹⁴² 834. L¹¹⁷ L¹⁴³ 835. L¹¹⁷ L¹⁴⁴ 836. L¹¹⁷ L¹⁴⁵837. L¹¹⁷ L¹⁴⁶ 838. L¹¹⁷ L¹⁴⁷ 839. L¹¹⁷ L¹⁴⁸ 840. L¹¹⁷ L¹⁴⁹ 841. L¹¹⁷L¹⁵⁰ 842. L¹¹⁷ L¹⁵¹ 843. L¹¹⁷ L¹⁵² 844. L¹¹⁷ L¹⁵³ 845. L¹¹⁷ L¹⁵⁴ 846.L¹¹⁷ L¹⁵⁵ 847. L¹¹⁷ L¹⁵⁶ 848. L¹¹⁷ L¹⁵⁷ 849. L¹¹⁷ L¹⁵⁸ 850. L¹¹⁷ L¹⁵⁹851. L¹¹⁸ L¹¹⁹ 852. L¹¹⁸ L¹²⁰ 853. L¹¹⁸ L¹²¹ 854. L¹¹⁸ L¹²² 855. L¹¹⁸L¹²³ 856. L¹¹⁸ L¹²⁴ 857. L¹¹⁸ L¹²⁵ 858. L¹¹⁸ L¹²⁶ 859. L¹¹⁸ L¹²⁷ 860.L¹¹⁸ L¹²⁸ 861. L¹¹⁸ L¹²⁹ 862. L¹¹⁸ L¹³⁰ 863. L¹¹⁸ L¹³¹ 864. L¹¹⁸ L¹³²865. L¹¹⁸ L¹³³ 866. L¹¹⁸ L¹³⁴ 867. L¹¹⁸ L¹³⁵ 868. L¹¹⁸ L¹³⁶ 869. L¹¹⁸L¹³⁷ 870. L¹¹⁸ L¹³⁸ 871. L¹¹⁸ L¹³⁹ 872. L¹¹⁸ L¹⁴⁰ 873. L¹¹⁸ L¹⁴¹ 874.L¹¹⁸ L¹⁴² 875. L¹¹⁸ L¹⁴³ 876. L¹¹⁸ L¹⁴⁴ 877. L¹¹⁸ L¹⁴⁵ 878. L¹¹⁸ L¹⁴⁶879. L¹¹⁸ L¹⁴⁷ 880. L¹¹⁸ L¹⁴⁸ 881. L¹¹⁸ L¹⁴⁹ 882. L¹¹⁸ L¹⁵⁰ 883. L¹¹⁸L¹⁵¹ 884. L¹¹⁸ L¹⁵² 885. L¹¹⁸ L¹⁵³ 886. L¹¹⁸ L¹⁵⁴ 887. L¹¹⁸ L¹⁵⁵ 888.L¹¹⁸ L¹⁵⁶ 889. L¹¹⁸ L¹⁵⁷ 890. L¹¹⁸ L¹⁵⁸ 891. L¹¹⁸ L¹⁵⁹ 892. L¹¹⁹ L¹²⁰893. L¹¹⁹ L¹²¹ 894. L¹¹⁹ L¹²² 895. L¹¹⁹ L¹²³ 896. L¹¹⁹ L¹²⁴ 897. L¹¹⁹L¹²⁵ 898. L¹¹⁹ L¹²⁶ 899. L¹¹⁹ L¹²⁷ 900. L¹¹⁹ L¹²⁸ 901. L¹¹⁹ L¹²⁹ 902.L¹¹⁹ L¹³⁰ 903. L¹¹⁹ L¹³¹ 904. L¹¹⁹ L¹³² 905. L¹¹⁹ L¹³³ 906. L¹¹⁹ L¹³⁴907. L¹¹⁹ L¹³⁵ 908. L¹¹⁹ L¹³⁶ 909. L¹¹⁹ L¹³⁷ 910. L¹¹⁹ L¹³⁸ 911. L¹¹⁹L¹³⁹ 912. L¹¹⁹ L¹⁴⁰ 913. L¹¹⁹ L¹⁴¹ 914. L¹¹⁹ L¹⁴² 915. L¹¹⁹ L¹⁴³ 916.L¹¹⁹ L¹⁴⁴ 917. L¹¹⁹ L¹⁴⁵ 918. L¹¹⁹ L¹⁴⁶ 919. L¹¹⁹ L¹⁴⁷ 920. L¹¹⁹ L¹⁴⁸921. L¹¹⁹ L¹⁴⁹ 922. L¹¹⁹ L¹⁵⁰ 923. L¹¹⁹ L¹⁵¹ 924. L¹¹⁹ L¹⁵² 925. L¹¹⁹L¹⁵³ 926. L¹¹⁹ L¹⁵⁴ 927. L¹¹⁹ L¹⁵⁵ 928. L¹¹⁹ L¹⁵⁶ 929. L¹¹⁹ L¹⁵⁷ 930.L¹¹⁹ L¹⁵⁸ 931. L¹¹⁹ L¹⁵⁹ 932. L¹²⁰ L¹²¹ 933. L¹²⁰ L¹²² 934. L¹²⁰ L¹²³935. L¹²⁰ L¹²⁴ 936. L¹²⁰ L¹²⁵ 937. L¹²⁰ L¹²⁶ 938. L¹²⁰ L¹²⁷ 939. L¹²⁰L¹²⁸ 940. L¹²⁰ L¹²⁹ 941. L¹²⁰ L¹³⁰ 942. L¹²⁰ L¹³¹ 943. L¹²⁰ L¹³² 944.L¹²⁰ L¹³³ 945. L¹²⁰ L¹³⁴ 946. L¹²⁰ L¹³⁵ 947. L¹²⁰ L¹³⁶ 948. L¹²⁰ L¹³⁷949. L¹²⁰ L¹³⁸ 950. L¹²⁰ L¹³⁹ 951. L¹²⁰ L¹⁴⁰ 952. L¹²⁰ L¹⁴¹ 953. L¹²⁰L¹⁴² 954. L¹²⁰ L¹⁴³ 955. L¹²⁰ L¹⁴⁴ 956. L¹²⁰ L¹⁴⁵ 957. L¹²⁰ L¹⁴⁶ 958.L¹²⁰ L¹⁴⁷ 959. L¹²⁰ L¹⁴⁸ 960. L¹²⁰ L¹⁴⁹ 961. L¹²⁰ L¹⁵⁰ 962. L¹²⁰ L¹⁵¹963. L¹²⁰ L¹⁵² 964. L¹²⁰ L¹⁵³ 965. L¹²⁰ L¹⁵⁴ 966. L¹²⁰ L¹⁵⁵ 967. L¹²⁰L¹⁵⁶ 968. L¹²⁰ L¹⁵⁷ 969. L¹²⁰ L¹⁵⁸ 970. L¹²⁰ L¹⁵⁹ 971. L¹²¹ L¹²² 972.L¹²¹ L¹²³ 973. L¹²¹ L¹²⁴ 974. L¹²¹ L¹²⁵ 975. L¹²¹ L¹²⁶ 976. L¹²¹ L¹²⁷977. L¹²¹ L¹²⁸ 978. L¹²¹ L¹²⁹ 979. L¹²¹ L¹³⁰ 980. L¹²¹ L¹³¹ 981. L¹²¹L¹³² 982. L¹²¹ L¹³³ 983. L¹²¹ L¹³⁴ 984. L¹²¹ L¹³⁵ 985. L¹²¹ L¹³⁶ 986.L¹²¹ L¹³⁷ 987. L¹²¹ L¹³⁸ 988. L¹²¹ L¹³⁹ 989. L¹²¹ L¹⁴⁰ 990. L¹²¹ L¹⁴¹991. L¹²¹ L¹⁴² 992. L¹²¹ L¹⁴³ 993. L¹²¹ L¹⁴⁴ 994. L¹²¹ L¹⁴⁵ 995. L¹²¹L¹⁴⁶ 996. L¹²¹ L¹⁴⁷ 997. L¹²¹ L¹⁴⁸ 998. L¹²¹ L¹⁴⁹ 999. L¹²¹ L¹⁵⁰ 1000.L¹²¹ L¹⁵¹ 1001. L¹²¹ L¹⁵² 1002. L¹²¹ L¹⁵³ 1003. L¹²¹ L¹⁵⁴ 1004. L¹²¹L¹⁵⁵ 1005. L¹²¹ L¹⁵⁶ 1006. L¹²¹ L¹⁵⁷ 1007. L¹²¹ L¹⁵⁸ 1008. L¹²¹ L¹⁵⁹1009. L¹²² L¹²³ 1010. L¹²² L¹²⁴ 1011. L¹²² L¹²⁵ 1012. L¹²² L¹²⁶ 1013.L¹²² L¹²⁷ 1014. L¹²² L¹²⁸ 1015. L¹²² L¹²⁹ 1016. L¹²² L¹³⁰ 1017. L¹²²L¹³¹ 1018. L¹²² L¹³² 1019. L¹²² L¹³³ 1020. L¹²² L¹³⁴ 1021. L¹²² L¹³⁵1022. L¹²² L¹³⁶ 1023. L¹²² L¹³⁷ 1024. L¹²² L¹³⁸ 1025. L¹²² L¹³⁹ 1026.L¹²² L¹⁴⁰ 1027. L¹²² L¹⁴¹ 1028. L¹²² L¹⁴² 1029. L¹²² L¹⁴³ 1030. L¹²²L¹⁴⁴ 1031. L¹²² L¹⁴⁵ 1032. L¹²² L¹⁴⁶ 1033. L¹²² L¹⁴⁷ 1034. L¹²² L¹⁴⁸1035. L¹²² L¹⁴⁹ 1036. L¹²² L¹⁵⁰ 1037. L¹²² L¹⁵¹ 1038. L¹²² L¹⁵² 1039.L¹²² L¹⁵³ 1040. L¹²² L¹⁵⁴ 1041. L¹²² L¹⁵⁵ 1042. L¹²² L¹⁵⁶ 1043. L¹²²L¹⁵⁷ 1044. L¹²² L¹⁵⁸ 1045. L¹²² L¹⁵⁹ 1046. L¹²³ L¹²⁴ 1047. L¹²³ L¹²⁵1048. L¹²³ L¹²⁶ 1049. L¹²³ L¹²⁷ 1050. L¹²³ L¹²⁸ 1051. L¹²³ L¹²⁹ 1052.L¹²³ L¹³⁰ 1053. L¹²³ L¹³¹ 1054. L¹²³ L¹³² 1055. L¹²³ L¹³³ 1056. L¹²³L¹³⁴ 1057. L¹²³ L¹³⁵ 1058. L¹²³ L¹³⁶ 1059. L¹²³ L¹³⁷ 1060. L¹²³ L¹³⁸1061. L¹²³ L¹³⁹ 1062. L¹²³ L¹⁴⁰ 1063. L¹²³ L¹⁴¹ 1064. L¹²³ L¹⁴² 1065.L¹²³ L¹⁴³ 1066. L¹²³ L¹⁴⁴ 1067. L¹²³ L¹⁴⁵ 1068. L¹²³ L¹⁴⁶ 1069. L¹²³L¹⁴⁷ 1070. L¹²³ L¹⁴⁸ 1071. L¹²³ L¹⁴⁹ 1072. L¹²³ L¹⁵⁰ 1073. L¹²³ L¹⁵¹1074. L¹²³ L¹⁵² 1075. L¹²³ L¹⁵³ 1076. L¹²³ L¹⁵⁴ 1077. L¹²³ L¹⁵⁵ 1078.L¹²³ L¹⁵⁶ 1079. L¹²³ L¹⁵⁷ 1080. L¹²³ L¹⁵⁸ 1081. L¹²³ L¹⁵⁹ 1082. L¹²⁴L¹²⁵ 1083. L¹²⁴ L¹²⁶ 1084. L¹²⁴ L¹²⁷ 1085. L¹²⁴ L¹²⁸ 1086. L¹²⁴ L¹²⁹1087. L¹²⁴ L¹³⁰ 1088. L¹²⁴ L¹³¹ 1089. L¹²⁴ L¹³² 1090. L¹²⁴ L¹³³ 1091.L¹²⁴ L¹³⁴ 1092. L¹²⁴ L¹³⁵ 1093. L¹²⁴ L¹³⁶ 1094. L¹²⁴ L¹³⁷ 1095. L¹²⁴L¹³⁸ 1096. L¹²⁴ L¹³⁹ 1097. L¹²⁴ L¹⁴⁰ 1098. L¹²⁴ L¹⁴¹ 1099. L¹²⁴ L¹⁴²1100. L¹²⁴ L¹⁴³ 1101. L¹²⁴ L¹⁴⁴ 1102. L¹²⁴ L¹⁴⁵ 1103. L¹²⁴ L¹⁴⁶ 1104.L¹²⁴ L¹⁴⁷ 1105. L¹²⁴ L¹⁴⁸ 1106. L¹²⁴ L¹⁴⁹ 1107. L¹²⁴ L¹⁵⁰ 1108. L¹²⁴L¹⁵¹ 1109. L¹²⁴ L¹⁵² 1110. L¹²⁴ L¹⁵³ 1111. L¹²⁴ L¹⁵⁴ 1112. L¹²⁴ L¹⁵⁵1113. L¹²⁴ L¹⁵⁶ 1114. L¹²⁴ L¹⁵⁷ 1115. L¹²⁴ L¹⁵⁸ 1116. L¹²⁴ L¹⁵⁹ 1117.L¹²⁵ L¹²⁶ 1118. L¹²⁵ L¹²⁷ 1119. L¹²⁵ L¹²⁸ 1120. L¹²⁵ L¹²⁹ 1121. L¹²⁵L¹³⁰ 1122. L¹²⁵ L¹³¹ 1123. L¹²⁵ L¹³² 1124. L¹²⁵ L¹³³ 1125. L¹²⁵ L¹³⁴1126. L¹²⁵ L¹³⁵ 1127. L¹²⁵ L¹³⁶ 1128. L¹²⁵ L¹³⁷ 1129. L¹²⁵ L¹³⁸ 1130.L¹²⁵ L¹³⁹ 1131. L¹²⁵ L¹⁴⁰ 1132. L¹²⁵ L¹⁴¹ 1133. L¹²⁵ L¹⁴² 1134. L¹²⁵L¹⁴³ 1135. L¹²⁵ L¹⁴⁴ 1136. L¹²⁵ L¹⁴⁵ 1137. L¹²⁵ L¹⁴⁶ 1138. L¹²⁵ L¹⁴⁷1139. L¹²⁵ L¹⁴⁸ 1140. L¹²⁵ L¹⁴⁹ 1141. L¹²⁵ L¹⁵⁰ 1142. L¹²⁵ L¹⁵¹ 1143.L¹²⁵ L¹⁵² 1144. L¹²⁵ L¹⁵³ 1145. L¹²⁵ L¹⁵⁴ 1146. L¹²⁵ L¹⁵⁵ 1147. L¹²⁵L¹⁵⁶ 1148. L¹²⁵ L¹⁵⁷ 1149. L¹²⁵ L¹⁵⁸ 1150. L¹²⁵ L¹⁵⁹

In one embodiment, a first device comprising a first organic lightemitting device is disclosed. The first organic light emitting devicecomprises an anode; a cathode; and an organic layer, disposed betweenthe anode and the cathode, comprising a compound having the structureaccording Formula I, L¹-Os-L²; wherein L¹ and L² are different; whereinL¹ and L² are independently selected from ligands having Formula II:

wherein Y¹, Y² and Y³ comprise C or N; wherein R³ and R⁴ may representmono-, or di-substitutions, or no substitution; wherein R⁵ may representmono-, di-, or tri-substitutions, or no substitution; wherein R¹ and R²are independently selected from the group consisting of alkyl andcycloalkyl; wherein R³, R⁴ and R⁵ are independently selected from thegroup consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl,aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof;wherein any two adjacent substituents of R¹, R², R³, R⁴ and R⁵ areoptionally joined to condense into a fused ring; and wherein the dashlines show the connection points to osmium.

In one embodiment of the first device, Y¹, Y² and Y³ comprise C. In oneembodiment, Y¹, Y² and Y³ are N. In one embodiment, R¹ and R² areindependently selected from the group consisting of methyl, ethyl,propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl,1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl,partially or fully deuterated variants thereof, and combinationsthereof.

In some embodiments of the first device, L¹ and L² are independentlyselected from ligands having Formula III:

wherein X¹, X², X³, X⁴, X⁵, X⁶, X⁷ and X⁸ comprise C or N. In someembodiments, X¹, X², X³, X⁴, X⁵, X⁶, X⁷ and X⁸ comprise C.

In some embodiments of the first device, the ligands having Formula IIare selected from the group consisting of L¹⁰¹ to L¹⁵⁹ defined herein.

In some embodiments of the first device, the first emitting compound isselected from the group consisting of Compounds 1 to 1159 defined inTable 1.

The first device can be one or more of a consumer product, an organiclight-emitting device, and/or a lighting panel.

The organic layer in the organic light emitting device can be anemissive layer and the compound can be an emissive dopant in someembodiments, while the compound can be a non-emissive dopant in otherembodiments.

The organic layer can also include a host. In some embodiments, the hostcan include a metal complex. In one embodiment, the host can be a metal8-hydroxyquinolate. The host can be a triphenylene containingbenzo-fused thiophene or benzo-fused furan. Any substituent in the hostcan be an unfused substituent independently selected from the groupconsisting of C_(n)H_(2n+1), OC_(n)H_(2n+1), OAr₁, N(C_(n)H_(2n+1))₂,N(Ar₁)(Ar₂), CH═CH—C_(n)H_(2n+1), C≡C—C_(n)H_(2n+1), Ar₁, Ar₁—Ar₂,C_(n)H_(2n)—Ar₁, or no substitution. In the preceding substituents n canrange from 1 to 10; and Ar₁ and Ar₂ can be independently selected fromthe group consisting of benzene, biphenyl, naphthalene, triphenylene,carbazole, and heteroaromatic analogs thereof.

The host can be a compound selected from the group consisting ofcarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene,azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, andaza-dibenzoselenophene. The “aza” designation in the fragments describedabove, i.e., aza-dibenzofuran, aza-dibenzonethiophene, etc., means thatone or more of the C—H groups in the respective fragment can be replacedby a nitrogen atom, for example, and without any limitation,azatriphenylene encompasses both dibenzo[f,h]quinoxaline anddibenzo[f,h]quinoline. One of ordinary skill in the art can readilyenvision other nitrogen analogs of the aza-derivatives described above,and all such analogs are intended to be encompassed by the terms as setforth herein. The host can include a metal complex. The host can be aspecific compound selected from the group consisting of:

and combinations thereof.

In yet another aspect of the present disclosure, a formulationcomprising the compound having a structure according to Formula I,L¹-Os-L², as defined herein, is disclosed. The formulation can includeone or more components selected from the group consisting of a solvent,a host, a hole injection material, hole transport material, and anelectron transport layer material, disclosed herein.

Combination with Other Materials

The materials described herein as useful for a particular layer in anorganic light emitting device may be used in combination with a widevariety of other materials present in the device. For example, emissivedopants disclosed herein may be used in conjunction with a wide varietyof hosts, transport layers, blocking layers, injection layers,electrodes and other layers that may be present. The materials describedor referred to below are non-limiting examples of materials that may beuseful in combination with the compounds disclosed herein, and one ofskill in the art can readily consult the literature to identify othermaterials that may be useful in combination.

HIL/HTL:

A hole injecting/transporting material to be used in the presentinvention is not particularly limited, and any compound may be used aslong as the compound is typically used as a hole injecting/transportingmaterial. Examples of the material include, but not limit to: aphthalocyanine or porphyrin derivative; an aromatic amine derivative; anindolocarbazole derivative; a polymer containing fluorohydrocarbon; apolymer with conductivity dopants; a conducting polymer, such asPEDOT/PSS; a self-assembly monomer derived from compounds such asphosphonic acid and silane derivatives; a metal oxide derivative, suchas MoO_(x); a p-type semiconducting organic compound, such as1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and across-linkable compounds.

Examples of aromatic amine derivatives used in HIL or HTL include, butnot limit to the following general structures:

Each of Ar¹ to Ar⁹ is selected from the group consisting aromatichydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl,triphenylene, naphthalene, anthracene, phenalene, phenanthrene,fluorene, pyrene, chrysene, perylene, azulene; group consisting aromaticheterocyclic compounds such as dibenzothiophene, dibenzofuran,dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene,benzoselenophene, carbazole, indolocarbazole, pyridylindole,pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole,oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine,pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine,indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole,benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline,quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine,phenazine, phenothiazine, phenoxazine, benzofuropyridine,furodipyridine, benzothienopyridine, thienodipyridine,benzoselenophenopyridine, and selenophenodipyridine; and groupconsisting 2 to 10 cyclic structural units which are groups of the sametype or different types selected from the aromatic hydrocarbon cyclicgroup and the aromatic heterocyclic group and are bonded to each otherdirectly or via at least one of oxygen atom, nitrogen atom, sulfur atom,silicon atom, phosphorus atom, boron atom, chain structural unit and thealiphatic cyclic group. Wherein each Ar is further substituted by asubstituent selected from the group consisting of hydrogen, deuterium,halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy,amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl,heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof.

In one aspect, Ar¹ to Ar⁹ is independently selected from the groupconsisting of:

wherein k is an integer from 1 to 20; X¹⁰¹ to X¹⁰⁸ is C (including CH)or N; Z¹⁰¹ is NAr¹, O, or S; Ar¹ has the same group defined above.

Examples of metal complexes used in HIL or HTL include, but not limit tothe following general formula:

wherein Met is a metal, which can have an atomic weight greater than 40;(Y¹⁰¹-Y¹⁰²) is a bidentate ligand, Y¹⁰¹ and Y¹⁰² are independentlyselected from C, N, O, P, and S; L¹⁰¹ is an ancillary ligand; k′ is aninteger value from 1 to the maximum number of ligands that may beattached to the metal; and k′+k″ is the maximum number of ligands thatmay be attached to the metal.

In one aspect, (Y¹⁰¹-Y¹⁰²) is a 2-phenylpyridine derivative. In anotheraspect, (Y¹⁰¹-Y¹⁰²) is a carbene ligand. In another aspect, Met isselected from Ir, Pt, Os, and Zn. In a further aspect, the metal complexhas a smallest oxidation potential in solution vs. Fc⁺/Fc couple lessthan about 0.6 V.

Host:

The light emitting layer of the organic EL device of the presentinvention preferably contains at least a metal complex as light emittingmaterial, and may contain a host material using the metal complex as adopant material. Examples of the host material are not particularlylimited, and any metal complexes or organic compounds may be used aslong as the triplet energy of the host is larger than that of thedopant. While the Table below categorizes host materials as preferredfor devices that emit various colors, any host material may be used withany dopant so long as the triplet criteria is satisfied.

Examples of metal complexes used as host are preferred to have thefollowing general formula:

wherein Met is a metal; (Y¹⁰³-Y¹⁰⁴) is a bidentate ligand, Y¹⁰³ and Y¹⁰⁴are independently selected from C, N, O, P, and S; L¹¹ is an anotherligand; k′ is an integer value from 1 to the maximum number of ligandsthat may be attached to the metal; and k′+k″ is the maximum number ofligands that may be attached to the metal.

In one aspect, the metal complexes are:

wherein (O—N) is a bidentate ligand, having metal coordinated to atoms Oand N.

In another aspect, Met is selected from Ir and Pt. In a further aspect,(Y¹⁰³-Y¹⁰⁴) is a carbene ligand.

Examples of organic compounds used as host are selected from the groupconsisting aromatic hydrocarbon cyclic compounds such as benzene,biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene,phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; groupconsisting aromatic heterocyclic compounds such as dibenzothiophene,dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran,benzothiophene, benzoselenophene, carbazole, indolocarbazole,pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole,oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole,pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine,oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine,benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline,cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine,pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine,benzofuropyridine, furodipyridine, benzothienopyridine,thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine;and group consisting 2 to 10 cyclic structural units which are groups ofthe same type or different types selected from the aromatic hydrocarboncyclic group and the aromatic heterocyclic group and are bonded to eachother directly or via at least one of oxygen atom, nitrogen atom, sulfuratom, silicon atom, phosphorus atom, boron atom, chain structural unitand the aliphatic cyclic group. Wherein each group is furthersubstituted by a substituent selected from the group consisting ofhydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl,alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester,nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof.

In one aspect, host compound contains at least one of the followinggroups in the molecule:

wherein R¹⁰¹ to R¹⁰⁷ is independently selected from the group consistingof hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl,arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylicacids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl,phosphino, and combinations thereof, when it is aryl or heteroaryl, ithas the similar definition as Ar's mentioned above k is an integer from0 to 20 or 1 to 20; k′″ is an integer from 0 to 20. X¹⁰¹ to X¹⁰⁸ isselected from C (including CH) or N. Z¹⁰¹ and Z¹⁰² is selected fromNR¹⁰¹, O, or S.

HBL:

A hole blocking layer (HBL) may be used to reduce the number of holesand/or excitons that leave the emissive layer. The presence of such ablocking layer in a device may result in substantially higherefficiencies as compared to a similar device lacking a blocking layer.Also, a blocking layer may be used to confine emission to a desiredregion of an OLED.

In one aspect, compound used in HBL contains the same molecule or thesame functional groups used as host described above.

In another aspect, compound used in HBL contains at least one of thefollowing groups in the molecule:

wherein k is an integer from 1 to 20; L¹⁰¹ is an another ligand, k′ isan integer from 1 to 3.

ETL:

Electron transport layer (ETL) may include a material capable oftransporting electrons. Electron transport layer may be intrinsic(undoped), or doped. Doping may be used to enhance conductivity.Examples of the ETL material are not particularly limited, and any metalcomplexes or organic compounds may be used as long as they are typicallyused to transport electrons.

In one aspect, compound used in ETL contains at least one of thefollowing groups in the molecule:

wherein R¹⁰¹ is selected from the group consisting of hydrogen,deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy,aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl,aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof, when it is aryl or heteroaryl, it has the similar definition asAr's mentioned above. Ar¹ to Ar³ has the similar definition as Ar'smentioned above. k is an integer from 1 to 20. X¹⁰¹ to X¹⁰⁸ is selectedfrom C (including CH) or N.

In another aspect, the metal complexes used in ETL contains, but notlimit to the following general formula:

wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinatedto atoms O, N or N, N; L¹⁰¹ is another ligand; k′ is an integer valuefrom 1 to the maximum number of ligands that may be attached to themetal.

In any above-mentioned compounds used in each layer of the OLED device,the hydrogen atoms can be partially or fully deuterated. Thus, anyspecifically listed substituent, such as, without limitation, methyl,phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated,and fully deuterated versions thereof. Similarly, classes ofsubstituents such as, without limitation, alkyl, aryl, cycloalkyl,heteroaryl, etc. also encompass undeuterated, partially deuterated, andfully deuterated versions thereof.

In addition to and/or in combination with the materials disclosedherein, many hole injection materials, hole transporting materials, hostmaterials, dopant materials, exciton/hole blocking layer materials,electron transporting and electron injecting materials may be used in anOLED. Non-limiting examples of the materials that may be used in an OLEDin combination with materials disclosed herein are listed in Table 2below. Table 2 lists non-limiting classes of materials, non-limitingexamples of compounds for each class, and references that disclose thematerials.

TABLE 2 MATERIAL EXAMPLES OF MATERIAL PUBLICATIONS Hole injectionmaterials Phthalocyanine and porphryin compounds

Appl. Phys. Lett. 69, 2160 (1996) Starburst triarylamines

J. Lumin. 72-74, 985 (1997) CF_(x) Fluorohydrocarbon polymer

Appl. Phys. Lett. 78, 673 (2001) Conducting polymers (e.g., PEDOT:PSS,polyaniline, polypthiophene)

Synth. Met. 87, 171 (1997) WO2007002683 Phosphonic acid and sliane SAMs

US20030162053 Triarylamine or polythiophene polymers with conductivitydopants

EP1725079A1

Organic compounds with conductive inorganic compounds, such asmolybdenum and tungsten oxides

US20050123751 SID Symposium Digest, 37, 923 (2006) WO2009018009 n-typesemiconducting organic complexes

US20020158242 Metal organometallic complexes

US20060240279 Cross-linkable compounds

US20080220265 Polythiophene based polymers and copolymers

WO 2011075644 EP2350216 Hole transporting materials Triarylamines (e.g.,TPD, α-NPD)

Appl. Phys. Lett. 51, 913 (1987)

U.S. Pat. No. 5,061,569

EP650955

J. Mater. Chem. 3, 319 (1993)

Appl. Phys. Lett. 90, 183503 (2007)

Appl. Phys. Lett. 90, 183503 (2007) Triaylamine on spirofluorene core

Synth. Met. 91, 209 (1997) Arylamine carbazole compounds

Adv. Mater. 6, 677 (1994), US20080124572 Triarylamine with(di)benzothiophene/ (di)benzofuran

US20070278938, US20080106190 US20110163302 Indolocarbazoles

Synth. Met. 111, 421 (2000) Isoindole compounds

Chem. Mater. 15, 3148 (2003) Metal carbene complexes

US20080018221 Phosphorescent OLED host materials Red hostsArylcarbazoles

Appl. Phys. Lett. 78, 1622 (2001) Metal 8-hydroxyquinolates (e.g., Alq₃,BAlq)

Nature 395, 151 (1998)

US20060202194

WO2005014551

WO2006072002 Metal phenoxybenzothiazole compounds

Appl. Phys. Lett. 90, 123509 (2007) Conjugated oligomers and polymers(e.g., polyfluorene)

Org. Electron. 1, 15 (2000) Aromatic fused rings

WO2009066779, WO2009066778, WO2009063833, US20090045731, US20090045730,WO2009008311, US20090008605, US20090009065 Zinc complexes

WO2010056066 Chrysene based compounds

WO2011086863 Green hosts Arylcarbazoles

Appl. Phys. Lett. 78, 1622 (2001)

US20030175553

WO2001039234 Aryltriphenylene compounds

US20060280965

US20060280965

WO2009021126 Poly-fused heteroaryl compounds

US20090309488 US20090302743 US20100012931 Donor acceptor type molecules

WO2008056746

WO2010107244 Aza-carbazole/DBT/DBF

JP2008074939

US20100187984 Polymers (e.g., PVK)

Appl. Phys. Lett. 77, 2280 (2000) Spirofluorene compounds

WO2004093207 Metal phenoxybenzooxazole compounds

WO2005089025

WO2006132173

JP200511610 Spirofluorene-carbazole compounds

JP2007254297

JP2007254297 Indolocabazoles

WO2007063796

WO2007063754 5-member ring electron deficient heterocycles (e.g.,triazole, oxadiazole)

J. Appl. Phys. 90, 5048 (2001)

WO2004107822 Tetraphenylene complexes

US20050112407 Metal phenoxypyridine compounds

WO2005030900 Metal coordination complexes (e.g., Zn, Al withN{circumflex over ( )}N ligands)

US20040137268, US20040137267 Blue hosts Arylcarbazoles

Appl. Phys. Lett, 82, 2422 (2003)

US20070190359 Dibenzothiophene/Dibenzo- furan-carbazole compounds

WO2006114966, US20090167162

US20090167162

WO2009086028

US20090030202, US20090017330

US20100084966 Silicon aryl compounds

US20050238919

WO2009003898 Silicon/Germanium aryl compounds

EP2034538A Aryl benzoyl ester

WO2006100298 Carbazole linked by non- conjugated groups

US20040115476 Aza-carbazoles

US20060121308 High triplet metal organometallic complex

U.S. Pat. No. 7,154,114 Phosphorescent dopants Red dopants Heavy metalporphyrins (e.g., PtOEP)

Nature 395, 151 (1998) Iridium(III) organometallic complexes

Appl. Phys. Lett. 78, 1622 (2001)

US2006835469

US2006835469

US20060202194

US20060202194

US20070087321

US20080261076 US20100090591

US20070087321

Adv. Mater. 19, 739 (2007)

WO2009100991

WO2008101842

U.S. Pat. No. 7,232,618 Platinum(II) organometallic complexes

WO2003040257

US20070103060 Osminum(III) complexes

Chem. Mater. 17, 3532 (2005) Ruthenium(II) complexes

Adv. Mater. 17, 1059 (2005) Rhenium (I), (II), and (III) complexes

US20050244673 Green dopants Iridium(III) organometallic complexes

Inorg. Chem. 40, 1704 (2001)

US20020034656

U.S. Pat. No. 7,332,232

US20090108737

WO2010028151

EP1841834B

US20060127696

US20090039776

U.S. Pat. No. 6,921,915

US20100244004

U.S. Pat. No. 6,687,266

Chem. Mater. 16, 2480 (2004)

US20070190359

US20060008670 JP2007123392

WO2010086089, WO2011044988

Adv. Mater. 16, 2003 (2004)

Angew. Chem. Int. Ed. 2006, 45, 7800

WO2009050290

US20090165846

US20080015355

US20010015432

US20100295032 Monomer for polymeric metal organometallic compounds

U.S. Pat. No. 7,250,226, U.S. Pat. No. 7,396,598 Pt(II) organometalliccomplexes, including polydentated ligands

Appl. Phys. Lett. 86, 153505 (2005)

Appl. Phys. Lett. 86, 153505 (2005)

Chem. Lett. 34, 592 (2005)

WO2002015645

US20060263635

US20060182992 US20070103060 Cu complexes

WO2009000673

US20070111026 Gold complexes

Chem. Commun. 2906 (2005) Rhenium(III) complexes

Inorg. Chem. 42, 1248 (2003) Osmium(II) complexes

U.S. Pat. No. 7,279,704 Deuterated organometallic complexes

US20030138657 Organometallic complexes with two or more metal centers

US20030152802

U.S. Pat. No. 7,090,928 Blue dopants Iridium(III) organometalliccomplexes

WO2002002714

WO2006009024

US20060251923 US20110057559 US20110204333

U.S. Pat. No. 7,393,599, WO2006056418, US20050260441, WO2005019373

U.S. Pat. No. 7,534,505

WO2011051404

U.S. Pat. No. 7,445,855

US20070190359, US20080297033 US20100148663

U.S. Pat. No. 7,338,722

US20020134984

Angew. Chem. Int. Ed. 47, 4542 (2008)

Chem. Mater. 18, 5119 (2006)

Inorg. Chem. 46, 4308 (2007)

WO2005123873

WO2005123873

WO2007004380

WO2006082742 Osmium(II) complexes

U.S. Pat. No. 7,279,704

Organometallics 23, 3745 (2004) Gold complexes

Appl. Phys. Lett. 74, 1361 (1999) Platinum(II) complexes

WO2006098120, WO2006103874 Pt tetradentate complexes with at least onemetal- carbene bond

U.S. Pat. No. 7,655,323 Exciton/hole blocking layer materialsBathocuprine compounds (e.g., BCP, BPhen)

Appl. Phys. Lett. 75, 4 (1999)

Appl. Phys. Lett. 79, 449 (2001) Metal 8-hydroxyquinolates (e.g., BAlq)

Appl. Phys. Lett. 81, 162 (2002) 5-member ring electron deficientheterocycles such as triazole, oxadiazole, imidazole, benzoimidazole

Appl. Phys. Lett. 81, 162 (2002) Triphenylene compounds

US20050025993 Fluorinated aromatic compounds

Appl. Phys. Lett. 79, 156 (2001) Phenothiazine-S-oxide

WO2008132085 Silylated five-membered nitrogen, oxygen, sulfur orphosphorus dibenzoheterocycles

WO2010079051 Aza-carbazoles

US20060121308 Electron transporting materials Anthracene- benzoimidazolecompounds

WO2003060956

US20090179554 Aza triphenylene derivatives

US20090115316 Anthracene-benzothiazole compounds

Appl. Phys. Lett. 89, 063504 (2006) Metal 8-hydroxyquinolates (e.g.,Alq₃, Zrq₄)

Appl. Phys. Lett. 51, 913 (1987) U.S. Pat. No. 7,230,107 Metalhydroxybenoquinolates

Chem. Lett. 5, 905 (1993) Bathocuprine compounds such as BCP, BPhen, etc

Appl. Phys. Lett. 91, 263503 (2007)

Appl. Phys. Lett. 79, 449 (2001) 5-member ring electron deficientheterocycles (e.g.,triazole, oxadiazole, imidazole, benzoimidazole)

Appl. Phys. Lett. 74, 865 (1999)

Appl. Phys. Lett. 55, 1489 (1989)

Jpn. J. Apply. Phys. 32, L917 (1993) Silole compounds

Org. Electron. 4, 113 (2003) Arylborane compounds

J. Am. Chem. Soc. 120, 9714 (1998) Fluorinated aromatic compounds

J. Am. Chem. Soc. 122, 1832 (2000) Fullerene (e.g., C60)

US20090101870 Triazine complexes

US20040036077 Zn (N{circumflex over ( )}N) complexes

U.S. Pat. No. 6,528,187

It is understood that the various embodiments described herein are byway of example only, and are not intended to limit the scope of theinvention. For example, many of the materials and structures describedherein may be substituted with other materials and structures withoutdeviating from the spirit of the invention. The present invention asclaimed may therefore include variations from the particular examplesand preferred embodiments described herein, as will be apparent to oneof skill in the art. It is understood that various theories as to whythe invention works are not intended to be limiting.

We claim:
 1. A compound having a structure according to Formula I:L¹-Os-L²; wherein L¹ and L² are different; wherein L¹ and L² areindependently selected from ligands having Formula II:

wherein: 1) for L¹, Y¹, Y² and Y³ comprise C and, for L², either (i) Y¹and Y³ comprises C and Y² is N, or (ii) Y¹ and Y³ are N, and Y²comprises C, or 2) for L¹, Y¹ and Y³ comprises C and Y² is N, and, forL², Y¹ and Y³ are N, and Y² comprises C; wherein R³ and R⁴ may representmono-, or di-substitutions, or no substitution; wherein R⁵ may representmono-, di-, or tri-substitutions, or no substitution; wherein R¹ and R²are independently selected from the group consisting of alkyl andcycloalkyl; wherein R³, R⁴ and R⁵ are independently selected from thegroup consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl,aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof;wherein any two adjacent substituents of R¹, R², R³, R⁴ and R⁵ areoptionally joined to condense into a fused ring; and wherein the dashlines show the connection points to osmium.
 2. The compound of claim 1,wherein, for L², Y¹ and Y³ comprise C, and Y² is N.
 3. The compound ofclaim 1, wherein, for L², Y¹ and Y³ are N, and Y² comprise C.
 4. Thecompound of claim 1, wherein each R¹ and R² is independently selectedfrom the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, andpartially or fully deuterated variants thereof.
 5. The compound of claim1, wherein each R¹ and R² is independently selected from the groupconsisting of methyl, ethyl, propyl, 1-methylethyl, butyl,1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fullydeuterated variants thereof, and combinations thereof.
 6. The compoundof claim 1, wherein L¹ and L² are independently selected from ligandshaving Formula III:

wherein each X¹, X², X³, X⁴, X⁵, X⁶, X⁷ and X⁸ independently comprises Cor N.
 7. The compound of claim 1, wherein each X¹, X², X³, X⁴, X⁵, X⁶,X⁷ and X⁸ comprises C.
 8. The compound of claim 1, wherein ligand L¹ isselected from the group consisting of:


9. The compound of claim 1, wherein R⁵ of L¹ is different from R⁵ of L².10. The compound of claim 1, wherein, for L¹, Y¹, Y² and Y³ comprise C,and, for L², Y¹ and Y³ comprises C and Y² is N
 11. The compound of claim1, wherein, for L¹, Y¹, Y² and Y³ comprise C, and, for L², Y¹ and Y³ areN, and Y² comprises C.
 12. The compound of claim 1, wherein for L¹, Y¹and Y³ comprises C and Y² is N, and, for L², Y¹ and Y³ are N, and Y²comprises C.
 13. A first device comprising a first organic lightemitting device, the first organic light emitting device comprising: ananode; a cathode; and an organic layer, disposed between the anode andthe cathode, comprising a compound having the structure accordingFormula IL¹-Os-L²; wherein L¹ and L² are different; wherein L¹ and L² areindependently selected from ligands having Formula II:

wherein: 1) for L¹, Y¹, Y² and Y³ comprise C and, for L², either (i) Y¹and Y³ comprises C and Y² is N, or (ii) Y¹ and Y³ are N, and Y²comprises C, or 2) for L¹, Y¹ and Y³ comprises C and Y² is N, and, forL², Y¹ and Y³ are N, and Y² comprises C; wherein R³ and R⁴ may representmono-, or di-substitutions, or no substitution; wherein R⁵ may representmono-, di-, or tri-substitutions, or no substitution; wherein R¹ and R²are independently selected from the group consisting of alkyl andcycloalkyl; wherein R³, R⁴ and R⁵ are independently selected from thegroup consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl,aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof,wherein any two adjacent substituents of R¹, R², R³, R⁴ and R⁵ areoptionally joined to condense into a fused ring; and wherein the dashlines show the connection points to osmium.
 14. The first device ofclaim 13, wherein the first device is a consumer product selected fromthe group consisting of light panels, flat panel displays, computermonitors, medical monitors, televisions, billboards, lights for interioror exterior illumination and/or signaling, heads up displays, fullytransparent displays, flexible displays, laser printers, telephones,cell phones, personal digital assistants (PDAs), laptop computers,digital cameras, camcorders, viewfinders, micro-displays, 3-D displays,vehicles, large area walls, theater or stadium screens, and signs. 15.The first device of claim 13, wherein the first device is an organiclight emitting device.
 16. The first device of claim 13, wherein theorganic layer is an emissive layer and the compound is an emissivedopant or a non-emissive dopant.
 17. The first device of claim 13,wherein the organic layer further comprises a host material.
 18. Thefirst device of claim 17, wherein the host material comprises atriphenylene containing benzo-fused thiophene or benzo-fused furan;wherein any substituent in the host material is an unfused substituentindependently selected from the group consisting of C_(n)H_(2n+1),OC_(n)H_(2n+1), OAr₁, N(C_(n)H_(2n+1))₂, N(Ar₁)(Ar₂),CH═CH—C_(n)H_(2n+1), C≡CC_(n)H_(2n+1), Ar₁, Ar₁—Ar₂, andC_(n)H_(2n)—Ar₁; wherein n is from 1 to 10; and wherein Ar₁ and Ar₂ areindependently selected from the group consisting of benzene, biphenyl,naphthalene, triphenylene, carbazole, and heteroaromatic analogsthereof.
 19. The first device of claim 17, wherein the host materialcomprises at least one chemical group selected from the group consistingof carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene,azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, andaza-dibenzoselenophene.
 20. The first device of claim 17, wherein thehost material is selected from the group consisting of:

and combinations thereof.